1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides

ABSTRACT

1-Alkyl-4-benzoyl-5-hydroxypyrazole compounds in which the benzoyl moiety is substituted in the 2-position with a halo, alkyl, or alkoxy group, in the 4-position with an alkylsulfonyl group, and in the 3-position with an optionally substituted phenyl group, for example, 1-(1,1-dimethylethyl)-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl-5-hydroxypyrazole, were prepared and found to be useful for the control of a variety of broadleaf and grassy weeds. The compounds can be applied either preemergently or postemergently and can be used to control undesirable vegetation selectively in small grain crops and turf or non-selectively.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser.No. 60/047469, filed May 23, 1997.

BACKGROUND OF THE INVENTION

This invention relates to novel 1-alkyl-4-benzoyl-5-hydroxypyrazolecompounds and to the use of these compounds as herbicides.

A number of 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and theirherbicidal utility have been disclosed in the art, for example, in U.S.Pat. Nos. 4,230,481, 4,063,925, 4,643,757, 4,744,815, 4,885,022,4,948,887, RE34,779, RE34,408, RE34,423, and PCT Application WO96/26206, published Aug. 29, 1996. The compounds disclosed in thesedocuments possess a variety of substituents on the benzoyl moiety. Whileherbicidal activity is present in these prior art compounds, it would behighly desirable to discover related compounds that are more active asherbicides, control a broader spectrum of undesirable vegetation, aremore selective to major crops, have a more desirable environmentalprofile, or have a more desirable toxicological profile.

SUMMARY OF THE INVENTION

It has now been found that1-(aliphatic)hydrocarbyl-4-benzoyl-5-hydroxypyrazole compoundspossessing an unsubstituted or substituted phenyl substituent in the3-position, an alkylsulfonyl substituent in the 4-position, and one of afew selected substituents in the 2-position of the benzoyl moiety arehighly active as herbicides, control a broad spectrum of undesirablevegetation, are selective to major crops, have desirable environmentalprofiles, and have desirable toxicological profiles.

The invention includes benzoylpyrazole compounds of Formula I: ##STR1##wherein X represents F, Cl, Br, CH₃, C₂ H₅, or OCH₃ ;

Y represents CH₃, C₂ H₅, CH(CH₃)₂, or cyclo-C₃ H₅ ;

Z represents H or benzyl (optionally possessing up to three ringsubstituents selected from F, Cl, Br, CN, CF₃, NO₂, CH₃, C₂ H₅, OCH₃,and OC₂ H₅);

W represents F, Cl, Br, CN, NO₂, OH, R", OR", OCOR", OCONHR", OSO₂ R",SR", SOR", SO₂ R", SO₂ OR", SO₂ NHR", SO₂ NR"₂, NHR", NR"₂, CO₂ R",CONHR", or CONR"₂ ; or any two adjacent W together represent thefragment --O(CH₂)_(m) O-- optionally mono to completely substituted withfluorine or methyl;

n represents 0, 1, 2, or 3;

m represents 1, 2, or 3;

R represents C₁ -C₄ alkyl, C₃ -C₄ alkenyl, or C₃ -C₄ alkynyl;

R' represents H, CH₂ OCH₃, or C₁ -C₃ alkyl;

R" represents C₁ -C₄ alkyl, C₂ -C₄ alkenyl, or C₂ -C₄ alkynyl eachoptionally mono to completely substituted with fluorine or monosubstituted with Cl, Br, O(C₁ -C₂ alkyl), or S(C₁ -C₂ alkyl); and

when Z represents H, the agriculturally acceptable salts and estersthereof.

The invention includes herbicidal compositions containing thebenzoylpyrazole compounds of Formula I in combination with anagriculturally acceptable adjuvant or carrier as well as a method of useof the compounds to kill or control undesirable vegetation byapplication of an herbicidal amount of the compound to the vegetation orto the locus of the vegetation. The use of the compounds to kill orcontrol weeds in rice, wheat, barley, and turf is a preferred utilityand postemergence application of the compounds to the undesirablevegetation is a preferred method of application.

The invention further includes substituted benzoic acid and otherintermediates that are useful in preparing the herbicidalbenzoylpyrazole compounds of Formula I.

DETAILED DESCRIPTION OF THE INVENTION

The herbicidal compounds of the present invention are benzoylpyrazolecompounds of Formula I: ##STR2## These compounds are characterized bypossessing a pyrazole heterocycle moiety substituted in the 1-positionwith an aliphatic hydrocarbyl group and in the 5-position with anhydroxy or benzyloxy group as well as in the 4-position with a benzoylmoiety. Substitution in the 3-position of the pyrazole ring with a loweralkyl moiety is optional. The benzoyl moiety is characterized by beingsubstituted in the 3-position with a phenyl or substituted phenyl group,in the 4-position with a lower alkylsulfonyl group, and in the2-position with a halo, lower alkyl or lower alkoxy group. The compoundsof Formula I, further, include the salt and ester compounds obtained byderivatization of the 5-position hydroxy substituent of the pyrazolemoiety.

The compounds of Formula I are some times named as (2,3,4-trisubstitutedphenyl) (1-alkyl-5-hydroxy-1H-pyrazol-4-yl)methanone compounds , but aremore often referred to in the art as 1-alkyl-4-(2,3,4-trisubstitutedbenzoyl)-5-hydroxypyrazole compounds. The latter terminology is usedherein. The compounds of Formula I wherein Z represents hydrogen aresometimes referred to as 1-alkyl-4-(2,3,4-trisubstitutedbenzoyl)-2-pyrazolin-5-one compounds; that is, as the keto tautomers ofthe formula illustrated.

The bond between the optionally substituted 3-phenyl substituent and thebenzoyl moiety of the compounds of Formula I is restricted in itsrotation due to steric factors and, as a result, in cases wherein thephenyl ring is asymmetrically substituted, the compounds often exist intwo optical isomer forms. The definition of the compounds of theinvention includes each of these isomers singly and when combined in anyproportion.

The most distinguishing feature of the compounds of Formula I is thepresence of the phenyl or substituted phenyl substituent in the3-position of the benzoyl moiety. The presence of such a substituent hasbeen found to impart unexpectedly beneficial herbicidal, environmental,and toxicological properties to benzoylpyrazole compounds.

Suitable substituents on the phenyl ring (W) include halo; cyano; nitro;hydroxy; optionally substituted lower alkyl, alkenyl, and alkynyl;optionally substituted lower alkoxy, alkenyloxy, and alkynyloxy;optionally substituted lower alkylcarbonyloxy, alkenylcarbonyloxy, andalkynylcarbonyloxy; optionally substituted lower alkylaminocarbonyloxy,alkenylaminocarbonyloxy, and alkynylaminocarbonyloxy; optionallysubstituted lower alkylsulfonyloxy, alkenylsulfonyloxy, andalkynylsulfonyloxy; optionally substituted lower alkylthio, alkenylthio,and alkynylthio; optionally substituted lower alkylsulfinyl,alkenylsulfinyl, and alkynylsulfinyl; optionally substituted loweralkylsulfonyl, alkenylsulfonyl, and alkynylsulfonyl; optionallysubstituted lower alkoxysulfonyl, alkenyloxysulfonyl, andalkynyloxysulfonyl; optionally substituted lower alkylaminosulfonyl,alkenylaminosulfonyl, and alkynylaminosulfonyl; optionally substituteddi(lower alkyl)aminosulfonyl, alkenylaminosulfonyl, andalkynylaminosulfonyl; optionally substituted lower alkylamino,alkenylamino, and alkynylamino; optionally substituted di(loweralkyl)amino, alkenylamino, and alkynylamino; optionally substitutedlower alkoxycarbonyl, alkenyloxycarbonyl, and alkynyloxycarbonyl;optionally substituted lower alkylaminocarbonyl, alkenylaminocarbonyl,and alkynylaminocarbonyl; and optionally substituted di(loweralkyl)aminocarbonyl, alkenylaminocarbonyl, and alkynylaminocarbonyl.There can be zero, one, or multiple such substituents present. Inaddition, any two adjacent W together can represent an optionallysubstituted ((poly)methylene)dioxy fragment. The following Wsubstituents are explicitly included in the compounds of Formula I: F,Cl, Br, CN, NO₂, OH, R", OR", OCOR", OCONHR", OSO₂ R", SR", SOR", SO₂R", SO₂ OR", SO₂ NHR", SO₂ NR"₂, NHR", NR"₂, CO₂ R", CONHR", and CONR"₂(wherein R" represents C₁ -C₄ alkyl, C₂ -C₄ alkenyl, or C₂ -C₄ alkynyleach optionally mono to completely substituted with fluorine or monosubstituted with Cl, Br, O(C₁ -C₂ alkyl), or S(C₁ -C₂ alkyl)) and, forany two adjacent W taken together, the fragment --O(CH₂)_(m) O--(wherein m represents 1, 2, or 3) optionally mono to completelysubstituted with fluorine or methyl. Compounds wherein W representsfluoro, chloro, methyl, ethyl, hydroxy, methoxy, ethoxy, 1-methylethoxy,2-propenyloxy (allyloxy), or methoxymethoxy are sometimes preferred andcompounds wherein W represents methoxy, ethoxy, 1-methylethoxy, ormethoxymethoxy are sometimes more preferred. Methoxy, ethoxy, andmethoxymethoxy are sometimes of special interest.

The compounds of Formula I can possess zero, one, two, or three Wsubstituents on the phenyl ring (n represents 0, 1, 2, or 3). Compoundspossessing one W substituent (n represents 1) are sometimes preferred.The W substituents can be in any position on the ring. Substituents inthe 4-position are often preferred. Compounds wherein Wn represents a4-methoxy, 4-ethoxy, 4-(l-methylethoxy), or 4-methoxymethoxy substituentare generally more preferred and those wherein Wn represents a4-methoxy, 4-ethoxy, or 4-methoxymethoxy substituent are sometimes ofspecial interest.

The invention includes compounds of Formula I wherein the benzoyl moietyis substituted in the 4-position (SO₂ Y) with a methylsulfonyl,ethylsulfonyl, 1-methylethylsulfonyl or cyclo-propylsulfonyl group.Methylsulfonyl groups (Y represents methyl) are typically preferred.

Compounds of Formula I substituted in the 2-position of the benzoylmoiety (X) with a halo, alkyl, or alkoxy group, such as fluoro, chloro,bromo, methyl, ethyl, and methoxy, are included in the invention.Compounds wherein X represents chloro and methyl are generally preferredand those wherein X represents methyl are usually especially preferred.Compounds wherein X and Y each represent methyl are often of specialinterest.

The invention includes compounds of Formula I wherein the pyrazolemoiety is substituted in the 1-position (R) with an aliphatichydrocarbyl group of 1 to 4 carbon atoms including compounds wherein Rrepresents a C₁ -C₄ alkyl, C₃ -C₄ alkenyl, or C₃ -C₄ alkynyl group.Compounds wherein R represents methyl, ethyl, 1-methylethyl,1,1-dimethylethyl, or cyclo-propyl are typically preferred. Compoundswherein R represents one of methyl, ethyl, and 1,1-dimethylethyl areoften independently more preferred depending on the specific herbicidalapplication contemplated. Compounds wherein R represents1,1-dimethylethyl are sometimes of special interest.

Compounds of Formula I that are unsubstituted in the 3-position of thepyrazole moiety (R' represents hydrogen) or are substituted in the3-position with methyl, ethyl, propyl, 1-methylethyl, cyclo-propyl, ormethoxymethyl are included in the invention. Compounds wherein R'represents hydrogen or methyl are typically preferred and compoundswherein R' represents hydrogen are typically more preferred. Compoundswherein R represents methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, orcyclo-propyl and R' represents hydrogen are often of interest.

The compounds of Formula I wherein Z represents hydrogen (5-hydroxycompounds) are believed to be the compounds that actually kill orcontrol undesirable vegetation and are typically preferred. Analogs ofsuch compounds that possess a derivatized hydroxy moiety which istransformed within plants or the environment to an hydroxy group possessessentially the same herbicidal effect and are within the scope of theinvention. Some specifically identified derivatives within thisdefinition include benzyl ethers (Z represents benzyl), which may besubstituted with one, two, or three compatible substituents. Suitablesubstituents include fluoro, chloro, bromo, cyano, trifluoromethyl,nitro, methyl, ethyl, methoxy, and ethoxy. Benzyl without substituentsis typically preferred.

Agriculturally acceptable salts of the compounds of Formula I, which areobtainable by treating a 5-hydroxy compound of Formula I with a base,such as a metal hydroxide, a metal carbonate, an amine, or an aminiumhydroxide compound, and esters, which are obtainable by treating a5-hydroxy compound of Formula I with an acid chloride, such as analkanoyl chloride, a benzoyl chloride, or an alkylsulfonyl chloride, arealso convertible to the hydroxy compound and are included in theinvention. Amine salts are sometimes preferred forms of the compounds ofFormula I because they are typically more water soluble and lendthemselves more readily to the preparation of desirable aqueous basedherbicidal compositions than other forms.

Compounds of Formula I wherein R represents 1,1-dimethylethyl, R'represents hydrogen, X represents methyl, Y represents methyl, and Wnrepresents a single 4-position substituent selected from methoxy,ethoxy, and methoxymethoxy are often highly desirable embodiments of theinvention.

The terms alkyl, alkenyl, and alkynyl as used herein includes straightchain, branched chain, and cyclic hydrocarbyl moieties. Thus, typicalalkyl groups are methyl, ethyl, 1-methylethyl, propyl, cyclo-propyl,1,1-dimethylethyl, cyclo-propylmethyl, 1-methyl-cyclo-propyl, and thelike. Methyl, ethyl, and 1,1-dimethylethyl are often preferred.Similarly, typical alkenyl groups include ethenyl, allyl (2-propenyl),and 1-methyl-2-propenyl and typical alkynyl groups include ethynyl andpropargyl. Typical alkyl, alkenyl, and alkynyl groups mono to completelysubstituted with fluorine or mono substituted with Cl, Br, O(C₁ -C₂alkyl), or S(C₁ -C₂ alkyl) include 2-chloroethyl, methoxymethyl,2-methoxyethyl, trifluoromethyl, difluoromethyl,1,1,2,2-tetrafluoroethyl, 2-ethylthioethyl, 3-chloroallyl,4-methylthio-2-butynyl, 2-ethoxy-1-methylethyl, and the like.

As noted above, the invention includes the agriculturally acceptablesalts and esters of compounds of Formula I wherein Z representshydrogen, which compounds are readily transformable into compoundswherein Z represents hydrogen and which possess essentially identicalherbicidal properties. The 5-position hydroxy group of the pyrazole ringof such compounds is weakly acidic and forms both salts and estersreadily. Agriculturally acceptable salts and esters are defined as thosesalts and esters of the 5-position hydroxy group of the pyrazole ring ofthe compounds of Formula I (wherein Z represents hydrogen) having acation or acid moiety that is not, itself, significantly herbicidal toany crop being treated and is not significantly deleterious to theapplicator, the environment, or the ultimate user of any crop beingtreated.

Suitable esters include those derived from optionally substitutedaliphatic and aromatic carboxylic acids, examples of which are C₁ -C₈alkylcarboxylic acids or C₃ -C₈ alkenylcarboxylic acids, and benzoicacid. Suitable esters further include alkylsulfonyl esters derived fromalkylsulfonic acids. C₁ -C₄ alkanoyl and benzoyl esters are generallypreferred.

Suitable cations include, for example, those derived from alkali oralkaline earth metals and those derived from ammonia and amines.Preferred cations include sodium, potassium, magnesium, and aminiumcations of the formula:

    R.sup.5 R.sup.6 R.sup.7 NH.sup.+

wherein R⁵, R⁶, and R⁷ each, independently represents hydrogen or C₁-C₁₂ alkyl, C₃ -C₁₂ cycloalkyl, or C₃ -C₁₂ alkenyl, each of which isoptionally substituted by one or more hydroxy, C₁ -C₈ alkoxy, C₁ -C₈alkylthio or phenyl groups, provided that R⁵, R⁶, and R⁷ are stericallycompatible. Additionally, any two of R⁵, R⁶, and R⁷ together mayrepresent an aliphatic difunctional moiety containing 1 to 12 carbonatoms and up to two oxygen or sulfur atoms. Salts of the compounds ofFormula I can be prepared by treatment of compounds of Formula I with ametal hydroxide, such as potassium hydroxide, or an amine, such asammonia, triethylamine, dimethylamine, hydroxyethylamine, bisallylamine,2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.

Some independently, specifically preferred compounds of the inventioninclude the following:1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methyl-sulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole,1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethoxyphenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(methoxymethoxy)phenyl)benzoyl)pyrazole,1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(2-propenyloxy)phenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(1-methylethoxy)phenyl)benzoyl)pyrazole,and1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-hydroxyphenyl)benzoyl)pyrazole.

The herbicidal compounds of the invention are exemplified by thecompounds listed in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    BENZOYLPYRAZOLE COMPOUNDS                                                       #STR3##                                                                                                                 Melting                                                                              Elem. Anal.                  Cpd.  Point Calc./Found                                                     No.                                                                              R      R'    Z    X   Y     Wn      Form ° C.                                                                          % C % H % N                __________________________________________________________________________     1 CH.sub.2 CH.sub.3                                                                    H     H    Cl  CH.sub.3                                                                            H       tan solid                                                                          240-241                                                                              56.4                                                                              4.23                                                                              6.92                          56.4 4.30 6.94                                                        2 C(CH.sub.3).sub.3 H H Cl CH.sub.3 H tan solid 262.5-264   58.3 4.89                                                                 6.47                          57.3 4.75 6.50                                                        3 CH.sub.2 CH.sub.3 H H Cl CH.sub.3 4-Cl yellow 240-241 52.0 3.76 6.38              solid  51.8 3.52 6.40                                                   4 C(CH.sub.3).sub.3 H H Cl CH.sub.3 4-Cl off-white 256-258 54.0 4.31                                                                  5.99                        solid  53.8 4.31 5.93                                                   5 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 H white 151-152 62.5 5.24                                                                   7.30                        solid  62.5 5.32 7.25                                                   6 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CH.sub.3 white 197-198                                                                    63.3 5.56 7.03              solid  63.1 5.58 7.01                                                   7 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CF.sub.3 off-white 155-156                                                                55.8 4.23 6.19              solid  55.5 4.14 6.22                                                   8 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-CH.sub.3 white 137.5-138.5                                                                63.3 5.56 7.03              solid  62.9 5.48 7.07                                                   9 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-Cl white 209-210 57.4 4.57                                                                6.69                        solid  57.2 4.57 6.92                                                  10 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.3 white 146.5-147.5                                                                60.9 5.35                                                                    6.76                        solid  60.4 5.26 7.01                                                  11 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-Cl white 160-161 57.4 4.57                                                                6.69                        solid  57.4 4.49 6.78                                                  12 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,5-diCl white   185-186.5                                                                          solid                                                                  13 CH(CH.sub.3                                                               ).sub.2 H H                                                                   CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.3                                                                   tan solid                                                                     174-175 61.7                                                                  5.64 6.54                                                                               61.8                                                                5.79 6.56                                                                      14 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.3                                                                   white 167-168                                                                 62.4 5.92 6.33              solid  62.7 5.40 6.40                                                  15 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.3 tan solid   211-212.5                                                                    60.5 5.03 7.00                59.6 4.99 7.04                                                       16 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 2-CH.sub.3 white 179-180                                                                    63.3 5.56 7.03              solid  63.3 5.72 7.14                                                  17 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 2-OCH.sub.3 tan solid                                                                       181-182.5 60.9                                                                5.35 6.76                                                                               59.7                                                                5.45 6.90                                                                      18 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3 2-F                                                                  lt yellow                                                                     176-177 59.7                                                                  4.76 6.96                                                                             solid                                                                 59.3 4.72 6.91       19 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 2-Cl lt yellow   173-174.5                                                                  57.4 4.57 6.69              solid  57.1 4.59 6.70                                                  20 C(CH.sub.3).sub.3 H H Cl CH.sub.3 4-OCH.sub.3 white 225-226 57.1                                                                    5.01 6.05                                                                             solid                                                                 56.9 5.04 6.12       21 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 2-F, lt yellow 151-152 58.3                                                                 4.89 6.43                                                                     4-OCH.sub.3                                                                   solid  57.7                                                                   4.90 6.35                                                                      22 CH(CH.sub.3                                                               )C.sub.2                                                                      H.sub.5 H H                                                                   CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.3                                                                   white 177-178                                                                 62.4 5.92 6.33              solid  61.9 6.04 6.38                                                  23 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 2-Cl, lt yellow 155.5-157                                                                   56.2 4.71 6.24             4-OCH.sub.3 solid  55.5 4.67 6.26                                       24 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CN off-white 192-193 61.6                                                                 4.68 10.3                                                                             solid                                                                 60.8 4.57 10.1       25 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CO.sub.2 CH.sub.3 white                                                                   159.5-160.5                                                                   59.7 5.01 6.33              solid  59.0 5.08 6.18                                                  26 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.2 OCH.sub.3 yellow                                                                140-142 59.5                                                                  5.44 6.30                                                                             powder                                                                 59.5 5.46                                                                    6.45                 27 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-OCH.sub.2 OCH.sub.3 yellow                                                                127-128 59.5                                                                  5.44 6.30                                                                     crystals  59.4                                                                5.39 6.41                                                                      28 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.2                                                                   OCH.sub.3                                                                     golden 139-141                                                                61.0 5.97 5.93              crystals  60.7 6.07 5.80                                               29 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-OCH.sub.3 yellow 157 60.9                                                                 5.35 6.76                                                                             solid                                                                 60.0 5.37 6.66       30 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-OCH.sub.2 CH.sub.3 lt                                                                     yellow 151                                                                    61.7 5.65 6.54              solid  61.5 5.70 6.61                                                  31 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-F, lt yellow 152 58.3 4.89                                                                6.48                       4-OCH.sub.3 solid  58.0 4.87 6.45                                       32 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-Cl, lt yellow 195                      4-OCH.sub.3 solid                                                       33 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.2 CH.sub.3 lt                                                                     yellow 164                                                                    61.7 5.65 6.54              solid  61.6 5.62 6.54                                                  34 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-OCH(CH.sub.3).sub.2 lt                                                                    yellow 165                                                                            solid                                                                  35 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-OCH(CH.sub.3)                                                               .sub.2 lt                                                                     yellow 133                                                                            solid                                                                  36 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.2                                                                   CH.sub.3 white                                                                110                         solid                                                                  37 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 4-OCH(CH.sub.3).sub.2 lt                                                                    yellow  97                                                                            solid                                                                  38 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3 4-                                                                   off-white                                                                     108-109 64.1                                                                  6.02 5.98                                                                     OCH.sub.2                                                                     CH═CH.sub.2                                                                powder  63.8                                                                 6.36 5.93                                                                      39 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      3-OCF.sub.3                                                                   yellow 74-76                                                                  53.8 4.09 5.98              solid  53.9 4.20 5.94                                                  40 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCF.sub.3 tan solid                                                                       116-118 53.8                                                                  4.09 5.98                                                                               53.6                                                                3.98 5.93                                                                      41 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      3-CH.sub.3,                                                                   white 202-204                                                                 58.3 4.89 6.47             4-Cl solid  58.0 4.77 6.51                                              42 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-Cl, tan solid 208-210 58.3                                                                4.89 6.47                                                                     4-CH.sub.3                                                                    58.1 4.85 6.32       43 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CH(CH.sub.3).sub.2 yellow                                                                  155-156.5                                                                    64.8 6.14 6.57              solid  64.7 6.11 6.73                                                  44 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CH.sub.2 CH.sub.3 yellow                                                                  167-169 64.1                                                                  5.86 6.79                                                                             solid                                                                 63.9 5.80 6.80       45 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-CH(CH.sub.3).sub.2 yellow                                                                 176-178 64.8                                                                  6.14 6.57                                                                             solid                                                                 64.7 6.12 6.62       46 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-CH.sub.2 CH.sub.3 yellow                                                                  164-166 64.1                                                                  5.86 6.79                                                                             solid                                                                 63.9 5.83 6.76       47 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-OCH.sub.3, tan solid                                                                      199-205 56.2                                                                  4.72 6.24                                                                            4-Cl                                                                   56.2 4.71 6.35       48 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-F yellow 195-197 59.7 4.76                                                                6.96                        powder  59.6 4.76 6.94                                                 49 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-F white 185-187                         powder                                                                 50 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-CH═CH.sub.2 orange                                                                    179-181                                                                               powder       51 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,5-diCH.sub.3 yellow                                                                       204-205                                                                               powder       52 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-Cl, orange 198-203 58.3                                                                   4.89 6.47                                                                     5-CH.sub.3                                                                    powder  58.0                                                                  4.79 6.65                                                                      53 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3 3-Cl,                                                                yellow 128-130                                                                55.0 4.15 6.41             4-F crystals  54.9 4.33 6.36                                            54 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,4-diCl off-white 217-219                                                                  53.0 4.00 6.18              powder  52.9 3.97 6.12                                                 55 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,4-diOCH.sub.3 yellow                                                                      192-194 59.5                                                                  5.44 6.30                                                                     crystals  59.4                                                                5.62 6.33                                                                      56 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3 4- lt                                                                yellow 144-146                                                                60.3 5.72 6.11             OCH.sub.2 CH.sub.2 OCH.sub.3 powder  60.0 5.67 6.22                     57 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3- yellow 166-168 60.3 5.72                                                                 6.11                       OCH.sub.2 CH.sub.2 OCH.sub.3 powder  60.0 5.78 6.18                     58 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 3,4-diOCH.sub.3 lt yellow                                                                   205-207 61.0                                                                  5.97 5.93                                                                     crystals  60.9                                                                6.66 5.98                                                                      59 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      3-CH.sub.3,                                                                   yellow 160-161                                                                61.7 5.65 6.54             4-OCH.sub.3 powder  61.4 5.74 6.68                                      60 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4- lt yellow  62.7 5.49 6.36             OCH.sub.2 CH═CH.sub.2 foam  62.3 5.46 6.34                          61 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3- lt yellow  62.7 5.49 6.36             OCH.sub.2 CH═CH.sub.2 foam  62.5 5.57 6.30                          62 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,4- yellow 166-167 58.9                                                                    4.71 6.54                                                                     OCH.sub.2 O--                                                                 powder  59.0                                                                  4.67 6.61                                                                      63 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3 3,4-                                                                 tan 218-219                                                                   60.5 5.30 6.14             OCH.sub.2 O-- powder  59.1 5.29 6.09                                    64 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3,4- tan 180-181 59.7 5.01                                                                  6.33                       OCH.sub.2 CH.sub.2 O-- powder  59.6 4.96 6.35                           65 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 3,4- tan 183-185 61.3 5.57                                                                  5.95                       OCH.sub.2 CH.sub.2 O-- powder  60.0 5.53 5.75                           66 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-SO.sub.2 CH.sub.3 white                                                                   232-233 54.5                                                                  4.79 6.06                                                                             powder                                                                 54.1 4.92                                                                    5.52                 67 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 4-SO.sub.2 CH.sub.3 lt                                                                      yellow 187-188                                                                56.3 5.34 5.71              powder  55.8 5.21 5.59                                                 68 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 3-CH.sub.3, yellow  63.1                                                                    6.18 6.14                                                                     4-OCH.sub.3                                                                   foam  63.1                                                                    6.22 6.06                                                                      69 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3 4-OH                                                                 white 203-205                                                                 60.0 5.03 7.00              solid  59.7 5.04 6.93                                                  70 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 4-OH white 254-256 61.7 5.65                                                                6.54                        solid  59.4 5.41 6.17                                                  71 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-Br white 113-115 51.8 4.13                                                                6.05                        solid  51.8 4.16 6.02                                                  72 C(CH.sub.3).sub.3 H CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3                                                                      4-OCH.sub.3                                                                   yellow  67.7                                                                  6.06 5.26                                                                             glass                                                                 67.4 6.07 5.17       73 C(CH.sub.3).sub.3 H COCH.sub.3 CH.sub.3 CH.sub.3 4-OCH.sub.3 white                                                                  160-163 62.0                                                                  5.82 5.78                                                                             powder                                                                 6.19 5.85                                                                    5.67                 74 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.2 CH.sub.2 F white                                                                177-181 59.2                                                                  5.19 6.27                                                                             solid                                                                 58.7 5.07 6.15       75 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.2 CH.sub.2 F tan                                                                  solid 146-150                                                                  76 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-OC(CH.sub.3).                                                               sub.3                77 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-OCH.sub.2 CH.tbd.CH                                                                        78 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-OCH.sub.2 -                                                                 cyclo-C.sub.3                                                                 H.sub.5                                                                        79 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-CH.sub.2                                                                    OCH.sub.3                                                                      80 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-CON(CH.sub.3)                                                               .sub.2                                                                         81 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-SO.sub.2                                                                    NHCH.sub.3                                                                     82 CH.sub.2                                                                  CH.sub.3 H H                                                                  CH.sub.3                                                                      CH.sub.3                                                                      4-N(CH.sub.3).s                                                               ub.2                 83 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 4-NO.sub.2                         84 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-CN                               85 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-C(CH.sub.3).sub.3                86 CH.sub.2 CH.sub.3 H H CH.sub.3 CH.sub.3 3-SCH.sub.3                        87 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 3-SO.sub.2 CH.sub.3                88 CH.sub.2 CH.sub.3 H H OCH.sub.3 CH.sub.3 4-OCH.sub.3                       89 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 4-OCHF.sub.22                        90 C(CH.sub.3).sub.3 H H CH.sub.3 CH.sub.3 4-OC(CH.sub.3).sub.3                                                                         91 C(CH.sub.3)                                                               .sub.3 H H                                                                    CH.sub.3                                                                      CH.sub.3                                                                      4-C(CH.sub.3).s                                                               ub.3                 92 CH.sub.3 CH.sub.3 Na F CH.sub.2 CH.sub.3 4-CH(CH.sub.3)OCH.sub.3                                                                     93 CH(CH.sub.3                                                               ).sub.2 H                                                                     COCH.sub.3                                                                    CH.sub.3                                                                      CH(CH.sub.3).su                                                               b.2 4-OCOCH.sub                                                               .3                   94 CH(CH.sub.3).sub.2 CH.sub.3 NH.sub.4 Br CH.sub.2 CH.sub.3 4-OCONHCH.s                                                               ub.3                 95 CH.sub.2 CH.tbd.CH CH(CH.sub.3).sub.2 CH.sub.2 C.sub.6 H.sub.5 F                                                                    CH.sub.2                                                                      CH.sub.3                                                                      4-OCH.sub.2                                                                   CF.sub.3                                                                       96 cyclo-C.sub                                                               .3 H.sub.5                                                                    CH.sub.2                                                                      OCH.sub.3                                                                     (CH.sub.3).sub.                                                               3 NH C.sub.2                                                                  H.sub.5                                                                       CH(CH.sub.3).su                                                               b.2 4-OCH.sub.2                                                                SCH.sub.3                                                                     97 CH.sub.2                                                                  CH═CH.sub.2                                                                CH.sub.2                                                                     CH.sub.3                                                                      SO.sub.2                                                                      CH.sub.3 Br                                                                   cyclo-C.sub.3                                                                 H.sub.5                                                                       3,5-diCH.sub.3,            4-OCH.sub.3                                                             98 cyclo-C.sub.3 H.sub.5 CH.sub.2 CH.sub.3 K OCH.sub.3 CH.sub.3                                                                        2,5-diCl,                                                                     4-OCH.sub.2                                                                   CH.sub.3           __________________________________________________________________________

The nuclear magnetic resonance (NMR) spectra of some the herbicidalcompounds of Formula I, which spectra are completely compatible with thestructures assigned to the compounds, are given in Table 2.

                  TABLE 2                                                         ______________________________________                                        SELECTED NMR SPECTRA                                                            Cpd.                                                                          No. .sup.1 H NMR (300 MHZ), δ ppm (from tetramethylsilane)            ______________________________________                                         5     CDCl.sub.3 : 8.20 (d, 1H), 7.58 (d, 1H), 7.40 (s, 1H), 7.24 (d,                 2H), 7.02 (d, 2H), 4.08 (q, 2H), 3.88 (s, 3H), 2.74 (s,                 3H), 2.08 (s, 3H), 1.47 (t, 3H)                                              12 CDCl.sub.3 : 8.20 (d, 1H), 7.64 (d, 1H), 7.48 (t, 1H), 7.38 (s,                   1H), 7.23 (d, 2H), 4.09 (q, 2H), 2.83 (s, 3H), 2.08 (s,                 3H), 1.47 (t, 3H)                                                            14 CDCl.sub.3 : 8.20 (d, 1H, J=8.3 Hz), 7.58 (d, 1H, J=8.3 Hz),                      7.34 (s, 1H), 7.24 (d, 2H, J=8.7 Hz), 7.02 (d, 2H, J=8.7                      Hz), 3.88 (s, 3H), 2.65 (s, 3H), 2.07 (s, 3H), 1.66 (s, 9H)                  17 CDCl.sub.3 : 8.20 (d, 1H), 7.59 (d, 1H), 7.46 (m, 1H), 7.41               (s,                                                                       1H), 7.23 (dd, 1H), 7.10 (dd, 1H), 7.01 (d, 1H), 4.10 (q,                     2H), 3.76 (s, 3H), 2.73 (s, 3H), 1.47 (t, 3H)                                19 CDCl.sub.3 : 8.21 (d, 1H), 7.64 (d, 1H), 7.4-7.5 (m, 4H),                   7.41 (s, 1H), 4.09 (q, 2H), 2.81 (s, 3H), 2.04 (s, 3H),                       1.47 (t, 3H)                                                                 21 CDCl.sub.3 : 8.19 (d, 1H), 7.63 (d, 1H), 7.39 (s, 1H), 7.26 (d,                   1H), 7.20 (d, 1H), 6.85 (dd, 1H), 6.76 (dd, 1H), 3.87 (s,                     3H), 2.80 (s, 3H), 2.09 (s, 3H), 1.47 (t, 3H)                          23 CDCl.sub.3 : 8.21 (d, 1H), 7.62 (d, 1H), 7.39 (s, 1H), 7.29 (d,                   1H), 7.06 (d, 1H), 6.97 (dd, 1H), 3.88 (s, 3H), 2.81 (s,                      3H), 2.06 (s, 3H), 1.47 (t, 3H)                                        24 CDCl.sub.3 : 8.21 (d, 1H), 7.88 (d, 1H), 7.67 (d, 1H), 7.46 (d,                   1H), 7.39 (s, 1H), 3.88 (s, 3H), 2.76 (s, 3H), 2.02 (s,                 3H), 1.47 (t, 3H)                                                            25 CDCl.sub.3 : 8.22 (d, 1H), 8.18 (d, 2H), 7.63 (d, 1H), 7.42 (d,                   2H), 7.39 (s, 1H), 3.96 (s, 3H), 2.71 (s, 3H), 1.47 (t, 3H)                  32 CDCl.sub.3 : 8.21 (d, 1H, J=8.4 Hz), 7.61 (d, 1H, J=8.4 Hz),                7.30 (m, 3H), 7.06 (d, 1H, J=8.7 Hz), 4.09 (q, 2H, J=7.3                      Hz), 3.98 (s, 3H), 2.74 (s, 3H), 2.08 (s, 3H), 1.47 (t, 3H,                   J=7.3 Hz)                                                              34 CDCl.sub.3 : 8.21 (d, 1H, J=8.4 Hz), 7.60 (d, 1H, J=8.4 Hz),                      7.37 (m, 2H), 6.99 (m, 1H), 6.85 (m, 2H), 4.57 (m, 1H),                 4.09 (q, 3H, J=7.3 Hz), 2.71 (s, 3H), 2.09 (s, 3H),                           1.47 (t, 3H, J=7.3 Hz), 1.35 (d, 6H, J=6.0 Hz)                               35 CDCl.sub.3 : 8.21 (d, 1H, J=8.4 Hz), 7.58 (d, 1H, J=8.4 Hz),                      7.40 (s, 1H), 7.22 (d, 2H, J=8.7 Hz), 6.99 (d, 2H, J=8.7                      Hz), 4.62 (m, 1H), 4.09 (q, 2H, J=7.3 Hz), 2.65 (s, 3H),                      2.08 (s, 3H), 1.47 (t, 3H, J=7.3 Hz), 1.39 (d, 6H, J=6.3                      Hz)                                                                    36 CDCl.sub.3 : 8.20 (d, 1H, J=8.4 Hz), 7.56 (d, 1H, J=8.4 Hz),                      7.34 (s, 1H), 7.23 (d, 2H, J=8.7 Hz), 7.01 (d, 2H, J=8.7                      Hz), 4.10 (q, 2H, J=7.0 Hz), 2.65 (s, 3H), 2.08 (s, 3H),                      1.66 (s, 9H), 1.46 (t, 3H, J=7.0 Hz)                                   37 CDCl.sub.3 : 8.20 (d, 1H, J=8.4 Hz), 7.58 (d, 1H, J=8.4 Hz),                      7.34 (s, 1H), 7.22 (d, 2H, J=6.6 Hz), 6.99 (d, 2H, J=6.6                      Hz), 4.63 (m, 1H), 2.65 (s, 3H), 2.09 (s, 3H), 1.67 (s,                 9H), 1.40 (d, 6H, J=6.2 Hz)                                                  49 CDCl.sub.3 : 8.23 (d, 1H, J=8 Hz), 7.62 (d, 1H, J=8 Hz),                    7.48 (m, 1H), 7.40 (s, 1H), 7.16 (m, 3H), 4.09 (q, 2H, J=7                    Hz), 2.74 (s, 3H), 2.06 (s, 3H), 1.47 (t, 3H, J=7 Hz)                        50 CDCl.sub.3 : 8.21 (d, 1H, J=8.4 Hz), 7.60 (d, 1H, J=8.4 Hz),                      7.54 (d, 2H, J=8 Hz), 7.40 (s, 1H), 7.28 (d, 2H, J=8 Hz),                     6.78 (dd, 1H, J=17.4, 10.7 Hz) 5.86 (d, 1H, J=17.4 Hz),                 5.35 (d, 1H, J=10.7 Hz), 4.09 (q, 2H, J=7.3 Hz), 2.68 (s,                     3H), 2.07 (s, 3H), 1.47 (t, 3H, J=7.3 Hz)                                    51 CDCl.sub.3 : 8.20 (d, 1H, J=8.0 Hz), 7.57 (d, 1H, J=8.0 Hz),                      7.39 (s, 1H), 7.09 (s, 1H), 6.92 (s, 2H), 4.09 (q, 2H,                  J=7.4 Hz), 2.68 (s, 3H), 2.37 (s, 6H), 2.06 (s, 3H),                          1.47 (t, 3H, J=7 Hz)                                                         60 CDCl.sub.3 : 8.20 (d, 1H, J=8 Hz), 7.58 (d, 1H, J=8 Hz),                    7.40 (bs, 1H), 7.22 (d, 2H, J=11 Hz), 7.02 (d, 2H, J=11                       Hz), 6.6 (ddd, 1H, J=5, 18, 15 Hz), 5.45 (d, 1H, J=15                         Hz), 5.32, d, 1H, J=10 hz), 4.58 (d, 2H, J=5 Hz),                             4.08 (q, 2H, J=5 Hz), 2.65 (s, 3H), 2.05 (s, 3H), 1.47 (t,                    3H, J=5 Hz)                                                                  70 CDCl.sub.3 : 8.20 (d, 1H, J=8 Hz), 7.58 (d, 1H, J=8 Hz),                    7.34 (s, 1H), 7.19 (d, 2H, J=9 Hz), 6.94 (d, 2H, J=9 Hz),                     2.69 (s, 3H), 2.08 (s, 3H), 1.67 (s, 9H)                                     72 CDCl.sub.3 : 8.15 (d, 1H, J=8.3 Hz), 7.45 (m, 6H), 7.24 (m, 3H),                  7.00 (m, 2H), 5.55 (s, 2H), 3.68 (s, 3H), 2.64 (s, 3H),                 2.02 (s, 3H), 1.57 (s, 9H)                                                 ______________________________________                                    

Compounds of Formula I can generally be prepared by the reaction of anappropriately substituted 3-phenylbenzoic acid compound of Formula II:##STR4## wherein X, Y, W, and n are as defined for compounds of FormulaI with an appropriate 5-hydroxypyrazole compound of Formula III:##STR5## wherein R and R' are as defined for compounds of Formula I.Preparative methods that can be readily adapted for this conversion aredisclosed, for example, in U.S. Pat. Nos. 4,063,925, 4,885,022, and4,986,845. One of these methods involves the conversion of the benzoicacid compound of Formula II to its acid chloride with thionyl chlorideor oxalyl chloride, the coupling of this acid chloride with a5-hydroxypyrazole compound of Formula III in the presence of atrialkylamine compound, such as triethylamine, and the rearrangement ofthe originally formed ester with a base and a cyanide ion catalyst,which is typically supplied by adding acetone cyano-hydrin. Anothermethod involves the reaction of a 3-phenylbenzoic acid compound ofFormula II with a 5-hydroxypyrazole compound of Formula III in thepresence of 1,3-dicyclohexylcarbodiimide and the subsequentisomerization of the originally formed ester with a base and a cyanideion catalyst, which is typically supplied by adding acetone cyanohydrin.The compounds of Formula I obtained by these procedures can be recoveredusing the methods exemplified herein and known in the art for relatedcompounds.

The 3-phenylbenzoic acid compounds of Formula II can be prepared by thereaction of an appropriate 3-iodobenzoic acid compound of Formula IV:##STR6## wherein X and Y are as defined for compounds of Formula I witha phenylboronic acid compound of Formula V: ##STR7## wherein W and n areas defined for compounds of Formula I, or with a substitutedphenylboronic acid anhydride trimer compound derived from aphenylboronic acid compound of Formula V (an optionally substitutedtriphenylboroxine compound). When X represents bromo, considerablediphenylation takes place, but the desired compound is produced and canbe recovered. The corresponding 3-bromobenzoic acid compounds canusually be used as well, but the results are generally not assatisfactory, especially when X represents bromo. The reaction isgenerally carried out by heating the reactants in an aqueous solvent,such as 1,2-dimethoxyethane, dioxane, or acetonitrile, in the presenceof a base, such as potassium carbonate, and a palladium(0) catalyst,such as tetrakis(triphenylphosphine)palladium-(0) or a mixture ofpalladium(II) acetate and tri-o-tolylphosphine. Reactions of this type,which are generally referred to in the art as Suzuki-Miyaura reactions,are discussed in detail in Chemical Reviews, 95, 2457-2483 (1995). Thecompounds of Formula II obtained by this method can be recovered byconventional means.

3-Iodobenzoic acid compounds of Formula IV can be prepared from thecorresponding 3-aminobenzoic acid compounds(3-amino-4-alkylsulfonyl-2-substituted-benzoic acid compounds) bydiazotization of the 3-aminobenzoic acid compound or an ester thereofand reaction of the diazonium salt formed with iodide ion. Suitableprocedures are exemplified herein and are well known in the art.3-Amino-4-alkylsulfonyl-2-substituted-benzoic acid compounds can beprepared by amination of a corresponding 3-halobenzoic acid compound orby reduction of the corresponding 3-nitrobenzoic acid compound usingmethods exemplified herein and well established in the art.

2-Substituted-3-phenylbenzoic acid compounds of Formula II can also beprepared from appropriate 4-substituted-2-aminobenzothiazole compoundsof Formula VI: ##STR8## wherein X is defined as for compounds of FormulaI. The method involves a sequence of chemical reactions which areindividually known in the art for some of the compounds and areexemplified herein. This reaction sequence is especially useful in thepreparation of compounds of Formula II wherein X represents chloro,bromo, or fluoro. The reaction sequence begins with the hydrolysis of acompound of Formula VI with a base, such as aqueous sodium hydroxide,and the alkylation of the product obtained with an alkyl halide, such asmethyl iodide. The 2-substituted-6-alkylthioaniline compounds obtainedcan be converted into the corresponding3-substituted-2-iodo(alkylthio)benzene compounds by diazotization andsubsequent reaction of the diazonium salt formed with iodide ion underreaction conditions well established in the art for this type ofreaction and exemplified herein. The3-substituted-2-iodo(alkylthio)benzene compounds obtained can beconverted into optionally substituted3-substituted-2-phenyl(alkylthio)benzene compounds(2-substituted-6-alkylthiobiphenyl compounds) of Formula VII: ##STR9##wherein X, Y, W, and n are as defined for compounds of Formula I bymeans of their reactions with optionally substituted phenylboronic acidcompounds or substituted phenylboronic acid anhydride trimer compounds.The Suzuki-Miyaura type reaction is generally carried out as discussedhereinabove and exemplified herein; that is, by heating the reactants inan aqueous polyether solvent, such as dioxane and 1,2-dimethoxyethane oraqueous acetonitrile, in the presence of a base, such as potassiumcarbonate, and a catalyst, such astetrakis(triphenylphosphine)palladium(0) or a mixture of palladium(II)acetate and tri-o-tolylphosphine. The optionally substituted3-substituted-2-phenyl(alkylthio)benzene compounds of Formula VIIobtained can be converted into optionally substituted4-bromo-3-substituted-2-phenyl(alkylsulfonyl)benzene compounds(2-substituted-3-bromo-6-alkylsulfonylbiphenyl compounds) of FormulaVIII: ##STR10## wherein X, Y, W, and n are as defined for compounds ofFormula I by consecutive treatments with bromine andmeta-chloroperbenzoic acid under reaction conditions exemplified hereinand well known in the art for aromatic ring bromination and sulfuroxidation reactions. The compounds of Formula VIII obtained can berecovered by conventional means. Compounds of Formula VIII can beconverted into optionally substituted methyl3-phenyl-4-alkylsulfonyl-2-substituted-benzoate compounds (methyl estersof compounds of Formula II) by treatment with carbon monoxide andmethanol in the presence of a trialkylamine compound, such astriethylamine, and a palladium(0) catalyst such astetrakis(triphenylphosphine)palladium(0) or palladium(II) acetate andtriphenylphosphine or tri-o-tolylphosphine. The reaction generally takesplace at temperatures of about 80° C. to 120° C. under carbon monoxidepressure. It is generally facilitated by carbon monoxide pressures ofabout 200 pounds per square inch (about 14,000 kilopascals) or higher.The product methyl esters can be recovered by conventional means.Considerable dicarbonylation takes place when X represents bromo, butthe desired product is formed and can be recovered. The product esterscan be converted into optionally substituted 3-phenylbenzoic acidcompounds of Formula II by hydrolysis using standard ester hydrolysisand acid recovery procedures well known in the art.

Phenylboronic acid compounds of Formula V can be prepared from thecorresponding bromobenzene or iodobenzene compounds by lithiation of thebromobenzene or iodobenzene compound with n-butyllithium, condensationof the phenyllithium compound obtained with tri(1-methylethyl) borate(triisopropoxyborane), and hydrolysis of the phenylboronate esterproduct obtained with aqueous hydrochloric acid. The general procedureis well known in the art and is exemplified herein. Butyllithium istypically added to a solution of a bromobenzene compound in a solvent,such as tetrahydrofuran, under anhydrous conditions at a temperature ofbelow -60° C. to form the corresponding phenyllithium compound andtri(l-methylethyl) borate is then added. The mixture is allowed to warmto near ambient temperature and aqueous hydrochloric acid is then addedto effect the hydrolysis. Phenylboronic acid and its substituted analogsare typically soluble in organic solvents, such as ether. Thesecompounds are sometimes recovered as the corresponding phenylboronicacid anhydride trimers instead of the acid. Phenylboronic acid compoundsand their anhydride trimers are readily interconvertible and reactinterchangeably with iodobenzene compounds to form biphenyl compounds inSuzuki-Miyaura type reactions.

Compounds of Formula I can alternatively be prepared by the reaction ofa1-hydrocarbyl-5-hydroxy-4-(2-substituted-3-iodo-4-alkylsulfonylbenzoyl)pyrazolecompound of Formula IX: ##STR11## wherein R, R', X, and Y are as definedfor compounds of Formula I with an optionally substituted phenylboronicacid compound of Formula V or a phenylboronic acid anhydride trimerthereof. The corresponding 3-bromo-benzoylpyrazole compounds cansometimes be used as well, but the results are generally not assatisfactory, especially when X represents bromo. This Suzuki-Miyauratype reaction is generally carried out as described hereinabove andexemplified herein. A compound of Formula IX, a compound of Formula V,potassium carbonate, and a catalytic amount oftetrakis(triphenylphoshine)-palladium(0) or palladium(II) acetate andtri-o-tolylphosphine are combined in aqueous dioxane,1,2-dimethoxyethane, or acetonitrile as a solvent and the mixture isheated at about 80° C. to 100° C. with good agitation. The compounds ofFormula I prepared by this procedure can be recovered by conventionalmeans.

Compounds of Formula IX can be prepared by the reaction of a3-iodobenzoic acid compound of Formula IV with a 5-hydroxypyrazolecompound of Formula III. The reactions can be carried out using themethods described hereinabove for the preparation of compounds ofFormula I by the reaction of compounds of Formula II with compounds ofFormula III.

Compounds of Formula I can additionally be prepared by the reaction of a4-iodo-3-substituted-2-(substituted-phenyl)(alkylsulfonyl)benzenecompound (a substituted 2-substituted-3-iodo-6-alkylsulfonylbiphenylcompound) of Formula X: ##STR12## wherein X, Y, W, and n are as definedfor compounds of Formula I with a 1-hydrocarbyl-5-hydroxypyrazolecompound of Formula III and carbon monoxide. The reaction is generallycarried out in the presence of a tertiary amine compound, such astriethylamine, and of a palladium(0) catalyst, such astetrakis(triphenylphosphine)palladium(0) or a mixture of palladium(II)acetate and tri-o-tolylphosphine. The analogous4-bromo-3-substituted-2-(substituted-phenyl)(alkylsulfonyl)benzenecompounds undergo this reaction and can often be used as well.Considerable amounts of by-product are typically obtained in thisprocedure when X represents bromo, but the desired compounds of FormulaI are obtained and can be recovered. Typically, the compound of FormulaX, the hydroxypyrazole compound of Formula III, the tertiary aminecompound, the catalyst, and a solvent, such as acetonitrile, arecombined and carbon monoxide gas is added to the mixture under pressure.The mixture is then heated under pressure at about 100° C. to about 120°C. for up to 30 hours. The reaction conditions employed, which areexemplified herein, are essentially the same as those disclosed in U.S.Pat. No. RE34,408 for the preparation of related compounds. Similarly,compounds of Formula I can be prepared from a4-iodo-3-substituted-2-(substituted-phenyl)(alkylthio)benzene compound(a 2-substituted-3-iodo-6-alkylthiobiphenyl compound) of Formula XI:##STR13## wherein X, Y, W, and n are as defined for compounds of FormulaI or a 4-bromo analog thereof. The compound of Formula XI, a compound ofFormula II, and carbon monoxide are heated in the presence of atrialkylamine compound, such as triethylamine, and a palladium(0)catalyst, such as tetrakis(triphenylphosphine)palladium(0) orpalladium(II) acetate and tri-o-tolylphosphine and the(4-alkylthiobenzoyl)pyrazole compound obtained as a product is oxidizedwith meta-chloroperbenzoic acid or another suitable oxidizing agent toconvert the alkylthio group (S--Y) to an alkylsulfonyl SO₂ --Y) group.

Compounds of Formula XI can be prepared from the corresponding2-substituted-3-(substituted-phenyl)-4-alkylthioaniline compounds ofFormula XII: ##STR14## wherein X, Y, W, and n are as defined forcompounds of Formula I by diazotization with nitrous acid and treatmentof the diazonium salt obtained with potassium iodide under reactionconditions well-known in the art and exemplified herein. Thecorresponding bromo compounds can be prepared analogously. Compounds ofFormula XI can also be made by conversion of the corresponding4-thiocyano compounds (compounds of Formula XI wherein Y represents CN)to 4-alkylthio compounds by treatment with sodium sulfide and an alkyliodide under conditions well established in the art for this type ofreaction.

Compounds of Formula X can be prepared from compounds of Formula XI byoxidation with meta-chloroperbenzoic acid or another suitable oxidizingagent using reaction conditions well known in the art and exemplifiedherein.

2-Substituted-3-(substituted-phenyl)-4-alkylthioaniline compounds ofFormula XII can be prepared by the reaction of the corresponding4-thiocyano compounds with sodium sulfide and an alkyl iodide underconditions well established in the art for such reactions andexemplified herein. The 4-thiocyano compounds required for this methodcan, in turn, be prepared by thiocyanation of corresponding2-substituted-3-(substituted-phenyl)aniline compounds of Formula XIII:##STR15## wherein X, W, and n are as defined for compounds of Formula Iunder reaction conditions exemplified herein and well established in theart for related reactions. Aniline compounds of Formula XIII can beprepared by reduction of the corresponding nitro compounds, which, inturn, can be prepared by phenylation of 2-substituted-3-iodonitrobenzenecompounds with optionally substituted phenylboronic acid compounds ofFormula V. Reaction conditions for these methods are exemplified hereinand are essentially the same as those described hereinabove for relatedSuzuki-Miyaura type conversions.

Compounds of Formula I wherein Z represents hydrogen can be convertedinto corresponding compounds of Formula I wherein Z representsoptionally substituted benzyl by treatment with an optionallysubstituted benzyl chloride or bromide using reaction conditionsexemplified herein and well known in the art and to promote similaretherification reactions. For example, approximately equimolar amountsof the reactants can be combined in an alcohol or a dipolar, aproticsolvent, a non-reactive base, such as a tertiary amine or an alkalimetal carbonate, added, and the mixture heated. Salts of compounds ofFormula I wherein Z represents hydrogen can be prepared by treatmentwith an equimolar amount of an appropriate metal hydroxide, amine, oraminium hydroxide compound. Esters of compounds of Formula I wherein Zrepresents hydrogen can be made by treatment with equimolar amounts ofan appropriate acid chloride compound and a tertiary amine compound,typically in an inert organic solvent. Reaction conditions known in theart for similar esterification reactions and exemplified herein can beused. In each case the compounds prepared can be recovered by standardtechniques.

The compounds of Formula I have been found to be useful preemergence andpostemergence herbicides. They can be employed at non-selective (higher)rates of application to control a broad spectrum of the vegetation in anarea or, in most cases, at selective (lower) rates of application forthe selective control of undesirable vegetation in grass crops, such ascorn, wheat, barley, rice, and turf as well as in broadleaf crops, suchas soybeans and cotton. It is usually preferred to employ the compoundspostemergence. It is further usually preferred to use the compounds tocontrol a broad spectrum of weeds, including grassy weeds, such asbarnyardgrass and giant foxtail, in crops, such as rice, wheat, barley,and turf. While each of the benzoylpyrazole compounds encompassed byFormula I is within the scope of the invention, the degree of herbicidalactivity, the crop selectivity, and the spectrum of weed controlobtained varies depending upon the substituents present. An appropriatecompound for any specific herbicidal utility can be identified by usingthe information presented herein and routine testing.

The term herbicide is used herein to mean an active ingredient whichkills, controls or otherwise adversely modifies the growth of plants. Anherbicidally effective or vegetation controlling amount is an amount ofactive ingredient which causes an adversely modifying effect andincludes deviations from natural development, killing, regulation,desiccation, retardation, and the like. The terms plants and vegetationinclude germinant seeds, emerging seedlings and established vegetation.

Herbicidal activity is exhibited by the compounds of the presentinvention when they are applied directly to the plant or to the locus ofthe plant at any stage of growth or before planting or emergence. Theeffect observed depends upon the plant species to be controlled, thestage of growth of the plant, the application parameters of dilution andspray drop size, the particle size of solid components, theenvironmental conditions at the time of use, the specific compoundemployed, the specific adjuvants and carriers employed, the soil type,and the like, as well as the amount of chemical applied. These and otherfactors can be adjusted as is known in the art to promote non-selectiveor selective herbicidal action. Generally, it is preferred to apply thecompounds of Formula I post-emergence to relatively immature undesirablevegetation to achieve the maximum control.

Application rates of about 1 to about 500 g/Ha are generally employed inpostemergence operations; for preemergence applications, rates of about10 to about 1000 g/Ha are generally employed. The higher ratesdesignated generally give non-selective control of a broad variety ofundesirable vegetation. The lower rates typically give selective controland, by judicious election, can be employed in the locus of crops.

The herbicidal compounds of the present invention are often best appliedin conjunction with one or more other herbicides to obtain control of awider variety of undesirable vegetation. When used in conjunction withother herbicides, the presently claimed compounds can be formulated withthe other herbicide or herbicides, tank mixed with the other herbicideor herbicides, or applied sequentially with the other herbicide orherbicides. Some of the herbicides that can be employed in conjunctionwith the compounds of the present invention include sulfonamides such asmetosulam, flumetsulam, cloransulam-methyl, diclosulam, andN-2,6-difluorophenyl-5-methoxy-8-fluoro[1,2,4]triazolo-[1,5-c]pyrimidine-2-sulfonamide,sulfonylureas such as chlorimuron, nicosulfuron and metsulfuron,imidazolidones such as imazaquin, imazethapyr and imazamox,phenoxyalkanoic acids such as 2,4-D and MCAA, pyridinyloxyacetic acidssuch as triclopyr and fluroxypyr, carboxylic acids such as clopyralidand dicamba, dinitroanilines such as trifluralin and pendimethalin, andother common herbicides including acifluorfen, bentazon, clomazone,fumiclorac, fluometuron, fomesafen, lactofen, linuron, isoproturon, andmetribuzin. They can, further, be used in conjunction with glyphosateand glufosinate. It is generally preferred to use the compounds of theinvention in combination with herbicides that are selective for the cropbeing treated and which complement the spectrum of weeds controlled bythese compounds at the application rate employed. It is furthergenerally preferred to apply the compounds of the invention andcomplementary other herbicides at the same time, either as a combinationformulation or as a tank mix.

The compounds of the present invention can generally be employed incombination with known herbicide safeners, such as cloquintocet,furilazole, dichlormid, benoxacor, flurazole, fenchlorazole-ethyl,mefenpyr, and fluxofenim, to enhance their selectivity. They canadditionally be employed to control undesirable vegetation in many cropsthat have been made tolerant to or resistant to them or to otherherbicides by genetic manipulation or by mutation and selection. Forexample, corn, wheat, rice, soybean, sugarbeet, cotton, canola, andother crops that have been made tolerant or resistant to compounds thatare quinone biosynthesis inhibitors in sensitive plants can be treated.Many glyphosate and glufosinate tolerant crops can be treated as well.

While it is possible to utilize the benzoylpyrazole compounds of FormulaI directly as herbicides, it is preferable to use them in mixturescontaining an herbicidally effective amount of the compound along withat least one agriculturally acceptable adjuvant or carrier. Suitableadjuvants or carriers should not be phytotoxic to valuable crops,particularly at the concentrations employed in applying the compositionsfor selective weed control in the presence of crops, and should notreact chemically with the compounds of Formula I or other compositioningredients. Such mixtures can be designed for application directly toweeds or their locus or can be concentrates or formulations which arenormally diluted with additional carriers and adjuvants beforeapplication. They can be solids, such as, for example, dusts, granules,water dispersible granules, or wettable powders, or liquids, such as,for example, emulsifiable concentrates, solutions, emulsions orsuspensions.

Suitable agricultural adjuvants and carriers that are useful inpreparing the herbicidal mixtures of the invention are well known tothose skilled in the art.

Liquid carriers that can be employed include water, toluene, xylene,petroleum naphtha, crop oil, acetone, methyl ethyl ketone,cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, propylene glycol monomethyl ether and diethyleneglycol monomethyl ether, methanol, ethanol, isopropanol, amyl alcohol,ethylene glycol, propylene glycol, glycerine, and the like. Water isgenerally the carrier of choice for the dilution of concentrates.

Suitable solid carriers include talc, pyrophyllite clay, silica,attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calciumcarbonate, bentonite clay, Fuller's earth, cotton seed hulls, wheatflour, soybean flour, pumice, wood flour, walnut shell flour, lignin,and the like.

It is usually desirable to incorporate one or more surface-active agentsinto the compositions of the present invention. Such surface-activeagents are advantageously employed in both solid and liquidcompositions, especially those designed to be diluted with carrierbefore application. The surface-active agents can be anionic, cationic,or nonionic in character and can be employed as emulsifying agents,wetting agents, suspending agents, or for other purposes. Typicalsurface-active agents include salts of alkyl sulfates, such asdiethanolammonium lauryl sulfate; alkylarylsulfonate salts, such ascalcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide additionproducts, such as nonylphenol-C₁₈ ethoxylate; alcohol-alkylene oxideaddition products, such as tridecyl alcohol-C₁₆ ethoxylate; soaps, suchas sodium stearate; alkylnaphthalenesulfonate salts, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions includecompatibilizing agents, antifoam agents, sequestering agents,neutralizing agents and buffers, corrosion inhibitors, dyes, odorants,spreading agents, penetration aids, sticking agents, dispersing agents,thickening agents, freezing point depressants, antimicrobial agents, andthe like. The compositions may also contain other compatible components,for example, other herbicides, plant growth regulants, fungicides,insecticides, and the like and can be formulated with liquid fertilizersor solid, particulate fertilizer carriers such as ammonium nitrate,urea, and the like.

The concentration of the active ingredients in the herbicidalcompositions of this invention is generally from about 0.001 to about 98percent by weight. Concentrations from about 0.01 to about 90 percent byweight are often employed. In compositions designed to be employed asconcentrates, the active ingredient is generally present in aconcentration from about 5 to about 98 weight percent, preferably about10 to about 90 weight percent. Such compositions are typically dilutedwith an inert carrier, such as water, before application. The dilutedcompositions usually applied to weeds or the locus of weeds generallycontain about 0.0001 to about 1 weight percent active ingredient andpreferably contain about 0.001 to about 0.05 weight percent.

The present compositions can be applied to weeds or their locus by theuse of conventional ground or aerial dusters, sprayers, and granuleapplicators, by addition to irrigation water, and by other conventionalmeans known to those skilled in the art.

EXAMPLES

The following Examples are presented to illustrate the various aspectsof this invention and should not be construed as limitations to theclaims.

1. Preparation of 3-Iodo-2-methyl-4-methylsulfonylbenzoic Acid

A) 3-Amino-2-methyl-4-methylsulfonylbenzoic Acid

A mixture of 79.0 g (grams) (320 mmol (millimole)) of3-chloro-2-methyl-4-methylsulfonylbenzoic acid, 1.0 g (12.6 mmol) ofcupric oxide, and 500 mL (milliliter) of concentrated aqueous ammoniawas heated at 180° C. for 17 hours in a stirred Parr reactor. Theresulting dark mixture was concentrated by evaporation under reducedpressure. The residue was acidified with 2N aqueous hydrochloric acidand the resulting mixture was extracted with ethyl acetate. The extractwas filtered and concentrated by evaporation under reduced pressure. Thesolid residue was mixed with hexane, recovered by filtration, and driedto obtain 50.0 g (68 percent of theory) of the title acid compound as alight tan powder melting at 197-198° C.

¹ H NMR(d₆ -DMSO) (dimethylsulfoxide): ppm 13.25(s, 1H), 7.50(d, 1H, J=8Hz), 6.92(d, 1H, J=8 Hz), 5.97(s, 2H), 3.12 (s, 3H), 2.22 (s, 3H)

B) Ethyl 3-Amino-2-methyl-4-methylsulfonylbenzoate

3-Amino-2-methyl-4-methylsulfonylbenzoic acid (50.0 g, 0.22 mol) wascombined with 500 mL of ethanol and 25 mL of concentrated sulfuric acidand the mixture was heated at reflux overnight. The resulting mixturewas partially concentrated by evaporation under reduced pressure and theresidue was poured onto ice. Water was added and the resulting mixturewas extracted with ethyl acetate. The extract was washed with diluteaqueous sodium hydroxide, filtered, and concentrated by evaporationunder reduced pressure to obtain 51.3 g (86 percent of theory) of theethyl ester as a tan solid melting at 108-109° C.

¹ H NMR(d₆ -DMSO): ppm 7.52(d, 1H, J=8 Hz), 6.92(d, 1H, J=8 Hz), 6.02(s,2H), 4.28(q, 2H, J=7 Hz), 3.14(s, 3H), 2.20(s, 3H), 1.28(t, 3H, J=7 Hz).

C) Ethyl 3-Iodo-2methyl-4-methylsulfonylbenzoate

A first solution of 54.0 g (0.21 mol) of ethyl3-amino-2-methyl-4-methylsulfonylbenzoate in 250 mL of concentratedaqueous hydrochloric acid was prepared and cooled to 0° C. with a dryice/2-propanol bath. A second solution of 21.7 g (0.315 mol) of sodiumnitrite in 40 mL of water was prepared and was added to the firstsolution dropwise with stirring and cooling (by adding dry ice to thebath) to keep the temperature below 0° C. The resulting yellow orangesolution containing some solids was added slowly with stirring to asolution of 52.3 g (0.315 mol) of potassium iodide in 500 mL of water.Nitrogen gas was evolved and the mixture turned dark brown.Dichloromethane was added to facilitate stirring and the mixture wasstirred for 30 min. Sodium sulfite was then added to remove some of thecolor and the resulting mixture was extracted three times withdichloromethane. The combined extracts were washed with water, driedover magnesium sulfate, and concentrated by evaporation under reducedpressure. The yellow solid residue was recrystallized from ethanol toobtain 68.5 g (89 percent of theory) of the title compound as paleyellow crystals. The compound melts at 104-105° C.

¹ H NMR(CDCl₃): ppm 8.13(d, 1H, J=8 Hz), 7.78(d, 1H, J=8 Hz), 4.41(q,2H, J=7 Hz), 3.32(s, 3H), 2.74(s, 3H), 1.38(t, 3H, J=7 Hz).

Ethyl 2-chloro-3-iodo-4-methylsulfonylbenzoate was prepared similarly.

C) 3-Iodo-2-methyl-4-methylsulfonylbenzoic Acid

A solution of 18.2 g (276 mmol) of 85 percent potassium hydroxide in 100mL of water was added to a mixture of 67.8 g (184 mmol) of ethyl3-iodo-2-methyl-4-methylsulfonylbenzoate in 300 mL of ethanol withstirring. After about 1 hour, all of the solids had dissolved and after2 hours the mixture was concentrated by evaporation under reducedpressure. The residue obtained was diluted with water and the solutionobtained was extracted with ether and then diluted with ethyl acetate.Aqueous hydrochloric acid (3N) was then added until the mixture wasacidic. The organic phase was separated and the aqueous phase was twiceextracted with ethyl acetate. The organic phase and extracts werecombined and washed with saturated aqueous sodium chloride solution,dried over magnesium sulfate, and concentrated by evaporation underreduced pressure. The 62.1 g (99 percent of theory) of colorless solidresidue was the title compound. The purified compound melts at 193° C.

¹ H NMR(d₆ -DMSO): ppm 13.80 (s, 1H), 7.98(d, 1H, J=8 Hz), 7.80(d, 1H,J=8 Hz), 3.40(s, 3H), 2.62(s, 3H).

2. Preparation of1-(1,1-Dimethylethyl)-5-hydroxy-4-(3-iodo-2-methyl-4-methylsulfonylbenzoyl)pyrazole

A solution of 8.4 9 (40 mmol) of 1,3-dicyclohexylcarbodiimide in 40 mLof acetonitrile was added to a mixture of 13.6 g (40 mmol) of3-iodo-2-methyl-4-methylsulfonylbenzoic acid and 5.6 g (40 mmol) of1-(1,1-dimethylethyl)-5-hydroxypyrazole in 80 mL of acetonitrile withstirring. The mixture was allowed to stir for 1 hour and was thenfiltered, washing the filter cake with a little acetonitrile.Triethylamine (16.8 mL, 120 mmol) and acetone cyanohydrin (1 mL, 10mmol) were added with stirring to the filtrate. After about 1.5 hour,dichloromethane was added and the resulting mixture was washed with amixture of 2N aqueous hydrochloric acid and saturated aqueous sodiumchloride. It was then concentrated by evaporation under reducedpressure. The residue obtained was dissolved in dichloromethane and theresulting solution was extracted with dilute aqueous sodium hydroxide.The aqueous extract was acidified with concentrated aqueous hydrochloricacid and the resulting mixture was extracted with dichloromethane. FiftymL of triethylamine was added to the dichloromethane extract and theresulting solution was washed with saturated aqueous sodium chloridesolution and then several times with 2N aqueous hydrochloric acid. Itwas then concentrated by evaporation under reduced pressure. The residuewas triturated with hexane to obtain 16.8 g (72.7 percent of theory ofthe title compound as a light yellow powder melting at 171-172° C.

Elemental Analysis C₁₆ H₁₉ N₂ IO₄ S; Calc.: %C, 41.6; %H, 4.14; %N,6.06; Found: %C, 41.7; %H, 4.16; %N, 6.00.

3. Preparation of1-Ethyl-5-hydroxy-4-(3-iodo-2-methyl-4-methylsulfonylbenzoyl)pyrazole

Thionyl chloride (20 mL) was added to a mixture of 62.1 g (182 mmol) of3-iodo-2-methyl-4-methylsulfonylbenzoic acid and 300 mL of1,2-dichloroethane and the mixture was heated to reflux with stirringfor 3 hours, absorbing the hydrogen chloride gas that evolved in anaqueous sodium hydroxide trap. The resulting solution was concentratedby evaporation under reduced pressure, diluted with 200 mL of tolueneand reconcentrated by evaporation under reduced pressure. The resultingresidue was dissolved in 100 mL of dichloromethane to obtain a firstsolution. A second solution was prepared by dissolving 22.3 g (270 mmol)of triethylamine and 24.7 g (270 mmol) of 1-ethyl-5-hydroxypyrazole in200 mL of dichloromethane. This solution was cooled in an ice bath andthe first solution was added to it dropwise with stirring and cooling.The resulting mixture was allowed to warm to ambient temperature and wasthen washed with cold 0.5N aqueous hydrochloric acid and then cold 5percent aqueous potassium carbonate. It was then dried over magnesiumsulfate and concentrated by evaporation under reduced pressure to obtain84.2 g of a nearly colorless solid. This solid was slurried in 400 mL ofdry acetonitrile and 1 mL (11 mmol) of acetone cyanohydrin and 37.7 g(270 mmol) of solid potassium carbonate were added. The mixture wasallowed to stir overnight and was then concentrated by evaporation underreduced pressure. The residue was dissolved in water and the solutionwas extracted with ether and then acidified with 3N aqueous hydrochloricacid. The resulting mixture was extracted three times withdichloromethane and the combined extracts were dried over magnesiumsulfate and concentrated by evaporation under reduced pressure. Thegummy residue was crystallized by adding ethanol, heating to reflux, andallowing the solution to cool to obtain 63.3 9 (68 percent of theory) ofthe title compound as yellow crystals. The compound melts at 149-150° C.

Elemental Analysis C₁₄ H₁₅ N₂ IO₄ S (typical sample); Calc.: %C, 38.7;%H, 3.48; %N, 6.45; %S, 7.38 Found: %C, 39.5; %H, 3.54; %N, 6.44; %S,7.49.

4. Preparation of2-Methyl-4-methylsulfonyl-3-(4-methylthiophenyl)benzoic Acid

A mixture of 5.8 g (17 mmol) of 3-iodo-2-methyl-4-methylsulfonylbenzoicacid, 4.0 g (23.8 mmol) of 4-methylthiophenylboronic acid, 11.7 g (85mmol) of potassium carbonate, 50 mL of acetonitrile, and 12 mL of waterwas prepared and purged with nitrogen gas with stirring. The catalystsystem, 190 mg (0.85 mmol) of palladium II acetate and 775 g (2.25 mmol)of tri-o-tolylphosphine, was added and the mixture was heated to refluxwith stirring for several hours. The mixture was then cooled, basifiedwith dilute aqueous sodium hydroxide solution, extracted with ether, andthen acidified with concentrated aqueous hydrochloric acid. Theresulting mixture was extracted with ether and the extract wasconcentrated by evaporation under reduced pressure. The residue wasdiluted with ethyl acetate and again concentrated by evaporation underreduced pressure. The residue was chromatographed on a preparative C-18high pressure liquid chromatography (HPLC) column eluting with a60:40:0.05 mixture of acetonitrile, water, and acetic acid. The productfractions were combined and extracted with ether. The ethereal extractswere concentrated by evaporation under reduced pressure and the residueobtained was diluted with ethyl acetate and again concentrated byevaporation under reduced pressure. The residue obtained was mixed withhexane and the insoluble solids were recovered by filtration and driedto obtain 2.2 g (39 percent of theory) of the title compound as a tanpowder melting at 178-179° C.

¹ H NMR(CDCl₃): ppm 8.20(d, 1H, J=8 Hz), 8.08(d, 1H, J=8 Hz), 7.35(d,2H, J=8 Hz), 7.20(d, 2H, J=8 Hz), 2.65(s, 3H), 2.55(s, 3H), 2.27(s, 3H).

2-Methyl-4-methylsulfonyl-3-(4-methoxyphenyl)-benzoic acid, a whitesolid, was prepared analogously.

5. Preparation of2-Methyl-4-methylsulfonyl-3-(4-methylsulfonylphenyl)benzoic Acid

A mixture of 2.2 g (6.5 mmol) of2-methyl-4-methylsulfonyl-3-(4-methylthiophenyl)benzoic acid, 2.2 mL(19.6 mmol) of 30 percent hydrogen peroxide, and 25 mL of acetic acidwas heated to 80° C. with stirring for 1 hour and was then allowed tostand overnight. The mixture was diluted with water, treated with sodiumbisulfite, and then extracted with a mixture of ether and ethyl acetate.The extract was concentrated by evaporation under reduced pressure andthe residue was diluted with dichloromethane. The resulting mixture wasfiltered and the solids that were collected were washed with ethylacetate. The filtrate was found to contain only about 0.5 g of impureproduct and was discarded. The solids were dissolved (a slow process) ina mixture of ethyl acetate and water and the organic phase was separatedand concentrated by evaporation under reduced pressure. The resultingsolid residue was diluted with hexane and the insoluble solids wererecovered by filtration and dried to obtain 2.1 g (88 percent of theory)of the title compound as a white powder melting at 214-215° C.

¹ H NMR (d₆ -DMSO): ppm 8.02 (m, 3H), 7.93 (d, 1H, J=8 Hz) 7.57(d, 2H,J=8 Hz), 3.32(s, 3H), 2.90(s, 3H), 2.02(s, 3H).

6. Preparation of 4-(Trifluoromethyloxy)phenylboronic Acid AnhydrideTrimer

A dilute solution of n-butyllithium was prepared by diluting 8.0 mL ofcommercial 2.5M solution with 20 mL of dry tetrahydrofuran (THF) and thesolution obtained was cooled to -90° C. with liquid nitrogen. A solutionof 5.0 g of 4-(trifluoromethoxy)bromobenzene in 5 mL of dry THF wasadded dropwise with stirring and cooling to keep the temperature atabout -90° C. After the addition, the mixture was allowed to stir for 30min and then 6.9 mL of tri(1-methylethyl) borate in 5 mL of dry THF wasadded dropwise with stirring and cooling to maintain the temperature atabout -90° C. The stirred mixture was allowed to warm to -70° C. and washeld there for 30 min. It was then allowed to warm to ambienttemperature over a 1-hour period. Twenty mL of 2N aqueous hydrochloricacid was added with stirring and the resulting mixture was extractedwith 40 mL of ether. The ether extract was washed with water and thenextracted with 20 mL of 2N aqueous sodium hydroxide solution. Theaqueous extract was acidified with concentrated aqueous hydrochloricacid and extracted with ether. The ether extract was washed withsaturated aqueous sodium chloride solution, dried over sodium sulfate,and concentrated by evaporation under reduced pressure. The residue wasremoved from the flask with the aid of cold pentane and recovered byfiltration to obtain 3.1 g of the title compound as a white solidmelting at 115-119° C. The solid was shown to be the anhydride trimer bymass spectrometry.

Elemental Analysis C₂₁ H₁₂ F₉ B₃ O₆ ; Calc.: %C, 44.7; %H, 2.14; Found:%C, 44.2; %H, 2.23.

The following substituted phenylboronic acid compounds and/or theanhydride trimers thereof were among those prepared analogously from thecorresponding bromobenzene compounds:

1) 3-(trifluoromethyloxy)phenylboronic acid, a white solid melting at74-77° C.;

2) 4-chloro-3-methylphenylboronic acid, a white solid melting at249-255° C.;

3) 3-chloro-4-methylphenylboronic acid, a white solid melting at180-190° C.;

4) 4-(methoxymethoxy)phenylboronic acid, a pale pink crystalline solidmelting at 130-133° C.;

5) 3-(methoxymethoxy)phenylboronic acid, a waxy solid;

6) 3,4-(ethylenedioxy)phenylboronic acid, a white powder melting at238-241° C.;

6) 3,4-(methylenedioxy)phenylboronic acid, a brown powder melting at237-240° C.;

7) 3,4-dichlorophenylboronic acid;

8) 3,4-dimethoxyphenylboronic acid;

9) 4-(2-methoxyethoxy)phenylboronic acid;

10) 3-(2-methoxyethoxy)phenylboronic acid;

11) 4-methoxy-3-methylphenylboronic acid;

12) 4-(2-propenyloxy)phenylboronic acid;

13) 3-(2-propenyloxy)phenylboronic acid;

14) 4-fluorophenylboronic acid;

15) 3-fluorophenylboronic acid;

16) 4-ethenylphenylboronic acid;

17) 3,5-dimethylphenylboronic acid, a white solid;

18) 3-chloro-5-methylphenylboronic acid;

19) 2-chlorophenylboronic acid, a white solid;

20) 3-fluoro-4-methoxyphenylboronic acid, a light yellow solid;

21) 3-chloro-4-methoxyphenylboronic acid, a light yellow solid meltingat 210° C.;

22) 4-ethoxyphenylboronic acid, a fluffy white solid melting at 165° C.;

23) 3-(1-methylethoxy)phenylboronic acid, a fluffy white solid meltingat 81° C.;

24) 4-(1-methylethoxy)phenylboronic acid, a fluffy white solid meltingat 75° C.;

26) 3-(1-methylethyl)phenylboronic acid, a white solid melting at 68-75°C.;

27) 4-(1-methylethyl)phenylboronic acid, a white solid melting at90-118° C.;

28) 4-ethylphenylboronic acid; a white solid melting at 90-130° C.;

29) 3-ethylphenylboronic acid; a white solid melting at 75-88° C.;

30) 4-chloro-3-methoxyphenylboronic acid, a light tan solid melting at107-150° C.;

31) 2-methylphenylboronic acid;

32) 2-methoxyphenylboronic acid;

33) 2-fluoro-4-methoxyphenylboronic acid; and

34) 3-methylphenylboronic acid.

7. Preparation of 2-Chloro-4-methylsulfonyl-3-phenylbenzoic Acid

A) 2-Chloro-6-methylthioaniline

A mixture of 36.0 g (196 mmol) of 2-amino-4-chlorobenzothiazole, 108 g(2.8 mmol) of sodium hydroxide, and 480 mL of water was heated at refluxwith stirring for 4.5 hours. The resulting mixture was cooled anddiluted with 180 mL of water. Six drops of tetrabutylammonium hydroxidewere added and then 22.5 mL (235 mmol) of dimethyl sulfate dissolved in50 mL of toluene was added dropwise over a 20-min period with stirring.The mixture was stirred another 30 min at ambient temperature. Ether wasadded and the phases were separated. The aqueous phase was extractedwith ether. The combined organic phase and extract were treated withdimethylamine to destroy excess dimethyl sulfate, washed with water,dried, and concentrated by evaporation under reduced pressure. Theresidual liquid was distilled at 1 mm (millimeter) Hg (130 Pascals)pressure and the 18 g (53 percent of theory) colorless liquid fractionboiling at 100° C. was collected and shown to be the title compound.

¹ H NMR(CDCl₃): ppm 7.26(d, 1H), 7.19(d, 1H), 6.64(dd, 1H), 4.65(brs,2H), 2.37(s, 3H).

B) 3-Chloro-2-iodo(methylthio)benzene

2-Chloro-6-methylthioaniline (15.0 g, 87 mmol) was dissolved in 200 mLof concentrated hydrochloric acid and the resulting solution was cooledto 0° C. to -10° C. with a dry ice/methanol bath. A solution of 8.9 g(130 mmol) of sodium nitrite in 30 mL of water was added dropwise withstirring and cooling to maintain the temperature below 0° C. Thesolution was then stirred for 20 min at 0C. A mixture of 22 g (130 mmol)of potassium iodide dissolved in 300 mL of water and 200 mL ofdichloromethane was prepared and the solution prepared above was addedto it in portions with stirring. The mixture was allowed to react for 20min at ambient temperature. A small amount of aqueous sodium bisulfitesolution was added and then the phases were separated. The organic phasewas washed twice with 2N aqueous hydrochloric acid and once withsaturated aqueous sodium chloride solution, dried over sodium sulfate,and concentrated by evaporation under reduced pressure. The residue wascrystallized with heptane and chromatographed on silica eluting with an85:15 mixture of hexane and dichloromethane to obtain 13.5 g of thetitle compound as a crystalline, low melting yellow solid.

¹ H NMR(CDCl₃): ppm 7.25(m, 2H), 6.92(m, 1H), 2.46(s, 3H)

C) 3-Chloro-2-phenyl(methylthio)benzene (2-Chloro-6-methylthiobiphenyl)

A mixture of 6.0 g (21 mmol) of 3-chloro-2-iodo(methylthio)benzene, 5.1g (42 mmol) of phenylboronic acid, 14 g (100 mmol) of potassiumcarbonate, 80 mL of 1,2-dimethoxyethane, and 75 mL of water was preparedand deaerated with a stream of nitrogen.Tetrakis(triphenylphosphine)palladium(0) (730 mg, 0.63 mmol) was addedand the mixture was heated at about 100° C. under nitrogen with stirringfor about 20 hours. Water and ether were added and the aqueous phase wasextracted with more ether. The ether phase and extract were combined,washed with saturated aqueous sodium chloride solution, dried oversodium sulfate, and concentrated by evaporation under reduced pressureand then in a Kugelrohr apparatus at 80° C. under 0.5 mm Hg (67 Pascals)pressure. The liquid residue was chromatographed on silica eluting withan 85:15 mixture of hexane and dichloromethane to obtain 4.3 g (87percent of theory) of the title compound as a colorless liquid.

¹ H NMR(CDCl₃): ppm 7.45(m, 3H), 7.25(m, 4H), 7.11(m, 1H) 2.34(s, 3H).

D) 3-Chloro-4-bromo-2-phenyl(methylthio)benzene(2-Chloro-3-bromo-6-methylthiobiphenyl)

A solution of 3.3 g (20 mmol) of bromine dissolved in 10 mL of1,2-dichloroethane was added dropwise with stirring to a solution of 4.0g (17 mmol) of 3-chloro-2-phenyl(methylthio)benzene in 50 mL of1,2-dichloroethane containing 3.1 g (19 mmol) of ferric chloride. Theresulting mixture was allowed to react for another 1.5 hour and thenanother about 1 g of bromine was added. After 15 min, aqueous sodiumbisulfite was added and the mixture was allowed to stand overnight. Theorganic phase was recovered, washed with water and with saturatedaqueous sodium chloride solution, dried over sodium sulfate, andconcentrated by evaporation under reduced pressure. The residue waschromatographed on silica eluting with a 5:1 mixture of hexane anddichloromethane to obtain 2.7 g (51 percent of theory) of the titlecompound as a colorless liquid.

¹ H NMR(CDCl₃): ppm 7.60(d, 1H, J=8.6 Hz), 7.47(m, 3H), 7.22(m, 2H),6.98(d, 1H, J=8.6 Hz), 2.32(s, 3H).

E) 3-Chloro-4-bromo-2-phenyl(methylsulfonyl)benzene(2-Chloro-3-bromo-6-methylsulfonylbiphenyl)

A solution of 2.5 g (8.0 mmol) of3-chloro-4-bromo-2-phenyl(methylthio)benzene in 75 mL of dichloromethanewas cooled with an ice bath and 5.7 g of meta-chloroperbenzoic acid wasadded in small portions with cooling and stirring. The mixture wasallowed to warm to ambient temperature and stir overnight and was thenheated to reflux for a short time. An aqueous solution of sodiumbisulfite was added and the mixture was made basic with sodiumcarbonate. The organic phase was separated, washed with dilute aqueoussodium bicarbonate solution, water, and saturated aqueous sodiumchloride solution, dried over sodium sulfate, and concentrated byevaporation under reduced pressure. The 3.0 g of residue was the titlecompound as a low melting white solid.

¹ H NMR(CDCl₃): ppm 8.04(d, 1H), 7.88(d, 1H), 7.50(m, 3H) 7.32(m, 2H),2.62(s, 3H)

F) Methyl 2-Chloro-4-methylsulfonyl-3-phenyl-benzoate

A mixture of 2.6 g (7.5 mmol) of3-chloro-4-bromo-2-phenyl(methylsulfonyl)benzene, 2.1 mL (15 mmol) oftriethylamine, 67 mg (0.3 mmol) of palladium(II) acetate, 0.26 g (0.6mmol) of 1,4-bis(diphenylphosphino)butane, and 120 mL of deaeratedmethanol were placed in a 200 mL Parr reactor. The mixture was purgedwith carbon monoxide and then pressured with carbon monoxide to 300 psi(pounds per square inch)(21,000 kiloPascals) and heated to 100° C. withstirring for 20 hours. The mixture was allowed to cool and wasconcentrated by evaporation under reduced pressure. The residue waspartitioned between water and a mixture of dichloromethane and ether.The organic phase was washed with dilute aqueous hydrochloric acid andthen saturated aqueous sodium chloride solution, dried over sodiumsulfate, and concentrated by evaporation under reduced pressure. Theresidue was 2.5 g of the title compound as a colorless, glassy solid.

¹ H NMR(CDCl₃): ppm 8.23(d, 1H), 7.83(d, 1H), 7.51(m, 3H) 7.33(m, 2H),3.98(s, 3H), 2.62(s, 3H).

G) 2-Chloro-4-methylsulfonyl-3-phenylbenzoic Acid

Methyl 2-chloro-4-methylsulfonyl-3-phenyl-benzoate was hydrolyzed withsodium hydroxide in aqueous methanol solution and recovered usingstandard methodology to obtain the title compound, a white solid, whichwas used as an intermediate without further analysis.

2-Chloro-4-methylsulfonyl-3-(4-chlorophenyl)-benzoic acid, a whitesolid;

¹ H NMR(d₆ -DMSO): ppm 8.15(d, 1H, J=8.3 Hz), 7.97(d, 1H, J=8.3 Hz),7.56(d, 2H, J=8.4 Hz), 7.38(d, 2H, J=8.4 Hz), 3.94(s, 3H);

and 2-chloro-4-methylsulfonyl-3-(4-methoxyphenyl)benzoic acid, a whitesolid;

¹ H NMR(d₆ -DMSO): ppm 8.13(d, 1H, J=8 Hz), 7.91(d, 1H, J=8 Hz), 7.26(d,2H, J=8 Hz), 7.06(d, 2H, J=8 Hz), 3.84(s, 3H), 2.83(s, 3H).

were among the 3-phenylbenzoic acid compounds prepared analogously.

8. Preparation of 4-Iodo-3-methyl-2-(2-methylphenyl)(methylsulfonyl)benzene (3-Iodo-2.2'-dimethyl-6-methylsulfonylbiphenyl)

A) 2-Methyl-3-(2-methylphenyl)nitrobenzene(2,2'-Dimethyl-3-nitrobiphenyl)

A mixture of 81 mg (0.36 mmol) of palladium(II) acetate and 330 mg (1.1mmol) of tri-o-tolylphosphine in 100 mL of dry 1,2-dimethoxyethane wasstirred for 15 min and then 3.2 g (12 mmol) of 3-iodo-6-nitrotoluene wasadded with stirring. After 15 min, 2.2 g (16 mmol) of2-methylphenylboronic acid in 15 mL of ethanol and 8.3 g (6.0 mmol) ofpotassium carbonate in 15 mL of water were added and the mixture washeated to 85° C. with stirring for 2 hours. The mixture was then allowedto cool and was diluted with water. The resulting mixture was extractedwith ether and the ethereal extract was filtered, washed with saturatedaqueous sodium chloride solution, dried over sodium sulfate, andconcentrated by evaporation under reduced pressure. The about 5 g ofresidue, which was the title compound in impure form, was used withoutpurification.

B) 2-Methyl-3-(2-methylphenyl)aniline (3-amino-2,2'-dimethylbiphenyl)

The about 5 g of 2-methyl-3-(2-methylphenyl)nitrobenzene obtained in A)was dissolved in 150 mL of deaerated ethanol and placed in a Parr shakerflask. About 1 g of 5 percent palladium on carbon catalyst was added andthe mixture was pressured with hydrogen. The hydrogenation was allowedto proceed overnight. The mixture was then filtered through diatomaceousearth and concentrated by evaporation under reduced pressure. Theresidue was dissolved in concentrated aqueous hydrogen chloride and thesolution was washed with ether. The hydrochloride salt of the titlecompound precipitated from this mixture and was recovered by filtrationand washed with ether. The recovered amine hydrochloride and filtratewere basified with aqueous sodium hydroxide and extracted with ether.The ether extract was washed with water and with saturated aqueoussodium chloride solution, dried over sodium sulfate, and concentratedunder reduced pressure to obtain 1.9 g of the title compound.

¹ H NMR(CDCl₃): ppm 7.4-7.0(m, 5H), 7.73(d, 2H), 7.62(d, 1H), 3.64(brs,2H), 2.07(s, 3H), 1.85(s, 3H).

C) 2-Methyl-3-(2-methylphenyl)-4-thiocyanoaniline(3-amino-2.2'-dimethyl-6-thiocyanobiphenyl)

A solution of 1.5 g (7.6 mmol) of 2-methyl-3-(2-methylphenyl)aniline and2.2 g of potassium thiocyanate in 25 mL of methanol was prepared andcooled to 0° C. A solution of 1.3 g (8.4 mmol) of bromine in 10 mL ofdichloromethane was added to this dropwise with stirring and cooling tokeep the temperature below 0° C. A precipitate began to formimmediately. After the addition was complete, the mixture was allowed towarm to ambient temperature and was stirred for another hour. Two mL ofsaturated sodium sulfite was added and the mixture was stirred for about5 min. It was then diluted with water and the resulting mixture wasextracted with ether. The ether phase was washed with water and withsaturated aqueous sodium chloride solution, dried over sodium sulfate,and concentrated by evaporation under reduced pressure. The 1.9 g (97percent of theory) of thick oil residue was the title compound.

¹ H NMR(CDCl₃): ppm 7.44(d, 1H), 7.30(m, 3H), 7.03(d, 1H) 6.76(d, 1H),3.91(brs, 2H), 2.02(s, 3H), 1.80(s, 3H).

D) 2-Methyl-3-(2-methylphenyl)-4-methylthioaniline(3-amino-2.2'-dimethyl-6-methylthiobiphenyl)

A solution of 2.0 g (7.9 mmol) of2-methyl-3-(2-methylphenyl)-4-thiocyanoaniline in 15 mL of ethanol wasadded dropwise over a 20-min period with stirring to a solution of 2.2 gof sodium sulfide nonahydrate (9.1 mmol) in 5 mL of water. The mixturewas stirred at ambient temperature for 2 hours and was then cooled withan ice/salt bath. A solution of 1.5 g (11 mmol) of methyl iodide in 5 mLof ethanol was added with stirring over a 10-min period. The mixture wasdiluted with water and the resulting mixture was extracted with ether.The ethereal extract was washed with water, dried over sodium sulfate,and concentrated by evaporation under reduced pressure. The 2.0 g ofresidue was the title compound of about 80 percent purity.

¹ H NMR(CDCl₃): ppm 7.44(d, 1H), 7.30(m, 3H), 7.03(d, 1H), 6.76(d, 1H),3.90(brs, 2H), 2.02(s, 3H), 1.80(s, 3H), 1.56(s, 3H).

E) 4-Iodo-3-methyl-2-(2-methylphenyl)(methylthio)benzene(3-iodo-2,2'-dimethyl-6-methylthiobiphenyl)

A solution of 2.0 g (8.2 mmol) of 85 percent purity2-methyl-3-(2-methylphenyl)-4-methylthioaniline in 3 mL ofdichloromethane was combined with 60 mL of concentrated aqueoushydrochloric acid and the mixture was stirred for 1 hour. It was thencooled to 5° C. A solution of 850 mg (12 mmol) of sodium nitrite in 10mL of water was added in portions with stirring and cooling. After 45min, this mixture was poured with stirring into a mixture of a solutionof 2.0 g (12 mmol) of potassium iodide in 100 mL of water and 75 mL ofdichloromethane and the combination was stirred for 30 min. Five mL ofsaturated sodium sulfite solution was then added with stirring and after20 min reaction time, the phases were separated. The organic phase waswashed with water and with saturated aqueous sodium chloride solution,dried over sodium sulfate, and concentrated under reduced pressure. The2.4 g (83 percent of theory) of oily residue obtained was the titlecompound in impure form.

F) 4-Iodo-3-methyl-2-(2-methylphenyl)(methylsulfonyl)benzene(3-Iodo-2.2'-dimethyl-6-methylsulfonylbiphenyl)

Solid meta-chloroperbenzoic acid (4.9 g, 17 mmol) was added in smallportions with stirring and cooling at 5-10° C. to a solution of 2.4 g(6.8 mmol) of 4-iodo-3-methyl-2-(2-methylphenyl)(methylthio)benzene in50 mL of dichloromethane. The mixture was allowed to warm to ambienttemperature and stir overnight. A few mL of aqueous sodium sulfitesolution was added with stirring and, after a negative starch-iodidetest was obtained, the phases were separated. The organic phase waswashed twice with dilute sodium bicarbonate, twice with water, and oncewith saturated aqueous sodium chloride solution and was then dried oversodium sulfate and concentrated by evaporation under reduced pressure.The residue was the title compound.

The following4-iodo-3-methyl-2-(substituted-phenyl)(methylsulfonyl)benzene compoundswere among those prepared analogously:

1) 4-iodo-3-methyl-2-(2-methoxyphenyl)(methylsulfonyl)benzene;

2) 4-iodo-3-methyl-2-(2-chlorophenyl)(methylsulfonyl)benzene;

3) 4-iodo-3-methyl-2-(2-fluorophenyl)(methylsulfonyl)benzene;

4) 4-iodo-3-methyl-2-(2-fluoro-4-methoxyphenyl)(methylsulfonyl)benzene;

5) 4-iodo-3-methyl-2-(2,4-dichlorophenyl)(methylsulfonyl)benzene; and

6) 4-iodo-3-methyl-2-(2-chloro-4-methoxyphenyl)(methylsulfonyl)benzene.

9. Preparation of1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-methylphenyl)benzoyl)pyrazole(Cpd. 16)

A mixture of 800 mg (2.1 mmol) of4-iodo-3-methyl-2-(2-methylphenyl)(methylsulfonyl)benzene, 700 mg (6.2mmol) of 1-ethyl-5-hydroxypyrazole, 1.2 mL (8.4 mmol) of triethylamine,24 mg (0.11 mmol) of palladium (II) acetate, 100 mg (0.33 mmol) oftri-o-tolylphosphine, and 20 mL of dry acetonitrile was placed in a 45mL Parr pressure reactor. The reactor was purged with carbon monoxideand then pressured to 300 psi (21,000 kiloPascals) with carbon monoxideand heated to 110° C. for 19 hours. The reactor was cooled and themixture was concentrated by evaporation under reduced pressure. Theresidue was chromatographed by preparative HPLC with a YMC CorporationODS-AQ column to separate the major product. The eluent, anacetonitrile/water mixture containing phosphoric acid, was extractedwith dichloromethane and the extract was washed with water, dried oversodium sulfate, and concentrated by evaporation under reduced pressure.The residue was dissolved in a minimum amount of dichloromethane andthen ether and hexane were added. The precipitate that formed wascollected by filtration and dried to obtain 200 mg of the title compoundas a white solid melting at 179-180° C.

The following benzoylpyrazole compounds were among those preparedanalogously:

1)1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-methoxyphenyl)benzoyl)pyrazole(Cpd. 17);

2)1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-fluorophenyl)benzoyl)pyrazole(Cpd. 18);

3)1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-chlorophenyl)benzoyl)pyrazole(Cpd. 19);

4)1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-fluoro-4-methoxyphenyl)benzoyl)pyrazole(Cpd. 21); and

5) 1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(2-chloro-4-methoxyphenyl)benzoyl)pyrazole (Cpd. 23).

10. Preparation of1-(1,1-dimethylethyl)-5-hydroxy-4-(2-chloro-4-methylsulfonyl-3-phenylbenzoyl)pyrazole(Cpd. 2)

2-Chloro-3-phenyl-4-methylsulfonylbenzoic acid (750 mg, 2.4 mmol),excess oxalyl chloride, and a few drops of N,N-dimethylformamide weredissolved in 1,2-dichloroethane and the mixture was allowed to reactwith stirring overnight. The mixture was then concentrated byevaporation under reduced pressure. The residue was taken up in about 10mL of dichloromethane and the resulting solution was cooled with an icebath. To this was added 410 mg (2.9 mmol) of1-(1,1-dimethylethyl)-5-hydroxypyrazole and about 2 mL of triethylamine.After about 1 hour, the mixture was diluted with water and with moredichloromethane and the phases were separated. The organic phase waswashed with dilute aqueous sodium bicarbonate, dried over sodiumsulfate, and concentrated by evaporation under reduced pressure. Theresidue was dissolved in 10 mL of anhydrous 1,2-dimethoxyethane and 1.3g (9.6 mmol) of sodium carbonate and then about 8 drops of acetonecyanohydrin were added. The mixture was allowed to react overnight andwas then diluted with water. The phases were separated and the aqueousphase was extracted with ether, acidified with aqueous hydrochloricacid, and then twice extracted with dichloromethane. The dichloromethaneextracts were combined and washed with saturated aqueous sodium chloridesolution, dried over sodium sulfate, and concentrated by evaporationunder reduced pressure. The 900 mg of residue was placed in 15 mL ofethanol and the mixture was heated and then cooled. The precipitate thatformed was collected by filtration, washed with ether, and dried in areduced pressure oven for 1 hour at 80° C. to obtain 682 mg (66 percentof theory) of the title compound as a tan solid melting at 262.5-264° C.

The following benzoylpyrazole compounds were among those prepared in ananalogous way:

1)1-ethyl-5-hydroxy-4-(2-chloro-4-methylsulfonyl-3-phenylbenzoyl)pyrazole(Cpd. 1);

2)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-chloro-4-methylsulfonyl-3-(4-chlorophenyl)benzoyl)pyrazole(Cpd. 4);

3)1-ethyl-5-hydroxy-4-(2-chloro-4-methylsulfonyl-3-(4-chlorophenyl)benzoyl)pyrazole(Cpd. 3);

4)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-chloro-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 20);

5)1-(1-methylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 13);

6)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 14);

7)1-methyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 15); and

8)1-(1-methylpropyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 22).

11. Preparation of1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methylsulfonylphenyl)benzoyl)pyrazole(Cpd. 67)

A solution of 560 mg (2.7 mmol) of 1,3-dicyclohexylcarbodiimide in 5 mLof acetonitrile was added with stirring to a mixture of2-methyl-4-methylsulfonyl-3-(4-methylsulfonylphenyl)benzoic acid and 378mg (2.7 mmol) of 1-(1,1-dimethylethyl)-5-hydroxypyrazole in 15 mL ofacetonitrile. The mixture was allowed to react for 1 hour and was thenfiltered. The solids were washed with a little acetonitrile.Triethylamine (1.13 mL, 8.1 mmol) and 274 microliters (2.7 mmol) ofacetone cyanohydrin were added with stirring to the combined filtrateand acetonitrile wash. After 3 hours, the mixture was diluted withdichloromethane and the resulting solution was washed with 2N aqueoushydrochloric acid, filtered, and concentrated by evaporation underreduced pressure. The residue was dissolved in the minimum amount of hotethanol and the solution was then cooled. The precipitate that formedwas collected by filtration and dried to obtain the title compound as apale yellow powder melting at 187-188° C.

1-Ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methylsulfonylphenyl)benzoyl)pyrazole(Cpd. 66) was prepared analogously.

12. Preparation of1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethoxyphenyl)benzoyl)pyrazole(Cpd. 36)

A mixture of 1.0 g (2.2 mmol) of1-(1,1-dimethylethyl)-5-hydroxy-4-(3-iodo-2-methyl-4-methylsulfonylbenzoyl)pyrazole,0.541 g (3.3 mmol) of 4-ethoxyphenylboronic acid, 0.607 g (4.4 mmol) ofpotassium carbonate, 0.025 g (0.11 mmol) of palladium(II) acetate, 0.100g (0.33 mmol) of tri-o-tolylphosphine, 25 mL of acetonitrile, and 3 mLof water was heated at reflux with stirring for 15 min. The resultingmixture was cooled and diluted with water. The mixture obtained wasextracted with ether and acidified with concentrated aqueoushydrochloric acid. The yellow precipitate that formed was collected byfiltration and recrystallized by dissolving in dichloromethane and thenadding hexane to obtain 800 mg (80 percent of theory) of the titlecompound as a white solid melting at 110° C.

The following benzoylpyrazole compounds were among those prepared in ananalogous way:

1)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 10);

2)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 14);

3)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(1-methylethoxyphenyl)benzoyl)pyrazole(Cpd. 35);

4)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(1-methylethoxyphenyl)benzoyl)pyrazole(Cpd. 37);

5)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(2-propenyloxyphenyl)benzoyl)pyrazole(Cpd. 60);

6)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(2-propenyloxyphenyl)benzoyl)pyrazole(Cpd. 38);

7)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(methoxymethoxyphenyl)benzoyl)pyrazole(Cpd. 26);

8)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(methoxymethoxyphenyl)benzoyl)pyrazole(Cpd. 28);

9)1-methyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 15);

10)1-(1-methylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 13);

11)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,4-methylenedioxyphenyl)benzoyl)pyrazole(Cpd. 62);

12)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,4-methylenedioxyphenyl)benzoyl)pyrazole(Cpd. 63);

13)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3-methoxyphenyl)benzoyl)pyrazole(Cpd. 29);

14)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-trifluoromethoxyphenyl)benzoyl)pyrazole(Cpd. 40);

15)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethylphenyl)benzoyl)pyrazole(Cpd. 44);

16)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3-chloro-4-methoxyphenyl)benzoyl)pyrazole(Cpd. 32);

17)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,4-dimethoxyphenyl)benzoyl)pyrazole(Cpd. 55);

18)1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,4-dimethoxyphenyl)benzoyl)pyrazole(Cpd. 58);

19)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-fluorophenyl)benzoyl)pyrazole(Cpd. 48);

20)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,5-dimethylphenyl)benzoyl)pyrazole(Cpd. 51);

21)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-phenylbenzoyl)pyrazole(Cpd. 5);

22)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methylphenyl)benzoyl)pyrazole(Cpd. 6);

23)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3-methylphenyl)benzoyl)pyrazole(Cpd. 8);

24)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-(trifluoromethyl)phenyl)benzoyl)pyrazole(Cpd. 7);

25)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-chlorophenyl)benzoyl)pyrazole(Cpd. 9); and

26)1-ethyl-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(3,5-dichlorophenyl)benzoyl)pyrazole(Cpd. 12).

13. Preparation of1-(1,1-dimethylethyl)-5-acetyloxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)-pyrazole(Cpd. 73)

A solution of 0.25 mL of acetyl chloride in 3 mL of dry dichloromethanewas added slowly under nitrogen at 0° C. with stirring to a solution of1.5 g (3.4 mmol) of1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazoleand 0.52 mL of triethylamine in about 20 mL of dry dichloromethane. Themixture was allowed to warm to ambient temperature and stir for 2 hoursand was then diluted with dichloromethane. The resulting solution wasextracted with saturated aqueous sodium bicarbonate solution and withwater, dried over magnesium sulfate, filtered, and concentrated byevaporation under reduced pressure. The residual yellow oil waschromatographed on silica gel eluting with a 50:50 mixture of ethylacetate and hexane. The product fractions were combined and concentratedby evaporation under reduced pressure to obtain 1.03 g (62 percent oftheory) of the title compound as a white powder melting at 160-163° C.

14. Preparation of1-(1,1-dimethylethyl)-5-benzyloxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole(Cpd. 72)

Benzyl chloride (1.1 mL) was added with stirring under nitrogen to amixture of 2.0 g (4.5 mmol) of1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazoleand 1.3 g of sodium carbonate in about 20 mL of dryN,N-dimethylformamide and the resulting mixture was allowed to stirovernight. Ethyl acetate was then added and the resulting mixture waswashed with water several times, dried over magnesium sulfate, filtered,and concentrated by evaporation under reduced pressure. The residualorange oil was chromatographed on silica eluting with an 80:20 mixtureand then a 60:40 mixture of hexane and ethyl acetate. The productfractions were combined and concentrated by evaporation under reducedpressure and dried to obtain 1.73 g (72 percent of theory) of the titlecompound as a yellow glass.

15. Evaluation of Postemergence Herbicidal Activity

Seeds of the desired test plant species were planted in Grace-SierraMetroMix® 360 planting mixture, which typically has a pH of 6.0 to 6.8and an organic matter content of about 30 percent, in plastic pots witha surface area of 64 square centimeters. When required to ensure goodgermination and healthy plants, a fungicide treatment and/or otherchemical or physical treatment was applied. The plants were grown for7-21 days in a greenhouse with an approximately 15 hr photoperiod whichwas maintained at about 23-29° C. during the day and 22-28° C. duringthe night. Nutrients and water were added on a regular basis andsupplemental lighting was provided with overhead metal halide 1000 Wattlamps as necessary. The plants were employed for testing when theyreached the first or second true leaf stage.

A weighed amount, determined by the highest rate to be tested, of eachtest compound was placed in a 20 mL glass vial and was dissolved in 4 mLof a 97:3 v/v (volume/volume) mixture of acetone and dimethyl sulfoxideto obtain concentrated stock solutions. If the test compound did notdissolve readily, the mixture was warmed and/or sonicated. Theconcentrated stock solutions obtained were diluted with an aqueousmixture containing acetone, water, isopropyl alcohol, dimethylsulfoxide, Atplus 411F crop oil concentrate, and Triton X-155 surfactantin a 48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain spray solutions ofknown concentration. The solutions containing the highest concentrationto be tested were prepared by diluting 2 mL aliquots of the stocksolution with 13 mL of the mixture and lower concentrations wereprepared by dilution of appropriate smaller portions of the stocksolution. Approximately 1.5 mL aliquots of each solution of knownconcentration were sprayed evenly onto each of the test plant pots usinga DeVilbiss atomizer driven by compressed air pressure of 2 to 4 psi(140 to 280 kiloPascals) to obtain thorough coverage of each plant.Control plants were sprayed in the same manner with the aqueous mixture.In this test an application rate of 1 ppm results in the application ofapproximately 1 g/Ha.

The treated plants and control plants were placed in a greenhouse asdescribed above and watered by sub-irrigation to prevent wash-off of thetest compounds. After 2 weeks the condition of the test plants ascompared with that of the untreated plants was determined visually andscored on a scale of 0 to 100 percent where 0 corresponds to no injuryand 100 corresponds to complete kill. Some of the compounds tested,application rates employed, plant species tested, and results are givenin Table 3.

                                      TABLE 3                                     __________________________________________________________________________    POSTMERGENCE HERBICIDAL ACTIVITY                                              __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm BWCHK BWCKB BWLMQ BWPIG BWVIO BWWBK BWWPT                           __________________________________________________________________________       1 62.5 40 90 100 100 40 100 60                                                2 15.6 45 90 85 50 85 80 55                                                   3 31.3 20 90 95 100 50 40 80                                                  4 31.3 60 80 90 85 80 20 85                                                   5 31.5 75 90 95 100 75 85 90                                                  6 62.5 85 95 90 100 80 75 100                                                 7 31.3 75 90 95 100 65 55 75                                                  8 62.5 80 95 80 100 75 65 100                                                 9 62.5 85 90 100 100 75 100 100                                              10 31.3 80 90 80 100 65 75 85                                                 11 31.3 70 95 98 100 70 65 95                                                 12 15.6 75 95 100 80 65 25 80                                                 13 15.6 75 95 100 100 75 95 90                                                14 7.8 65 90 80 65 65 70 75                                                   15 31.3 95 95 100 95 30 80 100                                                16 31.3 75 --  100 100 75 85 85                                               17 125 70 80 85 90 60 70 60                                                   18 125 40 85 90 90 70 85 70                                                   19 31.3 60 100 100 100 70 50 80                                               20 15.6 65 95 100 95 95 90 95                                                 21 62.5 80 95 100 100 70 90 95                                                22 125 40 70 100 30 60 70 50                                                  23 125 90 40 100 100 50 70 50                                                 24 62.5 60 30 90 100 60 70 30                                                 25 125 85 10 100 100 30 30 30                                               __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm GWBLG GWBRN GWCRB GWGFT GWROX GWWOT                                 __________________________________________________________________________       1 62.5 70 98 75 100 100 98                                                    2 15.6 90 98 85 90 95 98                                                      3 31.3 85 90 40 100 98 20                                                     4 31.3 98 90 80 93 98 95                                                      5 31.5 75 100 65 --  95 95                                                    6 62.5 15 95 75 -- 95 80                                                      7 31.3 80 95 75 100 100 75                                                    8 62.5 40 98 95 100 100 65                                                    9 62.5 80 80 70 70 100 70                                                    10 31.3 65 95 75 100 100 90                                                   11 31.3 70 85 65 80 100 95                                                    12 15.6 70 75 80 100 95 80                                                    13 15.6 80 100 80 100 100 100                                                 14 7.8 75 95 70 100 75 95                                                     15 31.3 40 75 75 80 75 85                                                     16 31.3 75 80 80 100 100 100                                                  17 125 50 85 80 90 90 75                                                      18 125 60 95 80 85 100 80                                                     19 31.3 75 70 75 80 100 100                                                   20 15.6 80 95 80 100 100 95                                                   21 62.5 40 95 60 80 95 70                                                     22 125 50 90 80 90 90 85                                                      23 125 10 70 10 10 100 10                                                     24 62.5 100 90 60 80 100 100                                                  25 125 10 70 10 70 20 10                                                    __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm BWCHK BWCKB BWLMQ BWPIG BWVIO BWWBK BWWPT                           __________________________________________________________________________      26 31.3 80 95 100 100 45 55 90                                                27 31.3 80 95 100 100 70 75 95                                                28 15.6 65 80 75 75 40 20 70                                                  29 31.3 75 90 85 100 75 75 90                                                 30 125 50 70 100 100 50 40 80                                                 31 15.6 70 95 100 100 60 80 90                                                32 31.3 75 90 100 95 65 80 90                                                 33 31.3 85 95 100 100 70 70 90                                                34 31.3 80 95 100 100 80 60 85                                                35 125 70 85 90 100 60 50 90                                                  36 15.6 75 95 100 100 75 75 75                                                37 15.6 70 80 100 75 50 55 80                                                 38 31.3 75 100 100 70 25 45 55                                                39 125 60 80 90 100 50 70 100                                                 40 62.5 70 90 95 100 40 30 50                                                 41 62.5 60 60 90 100 50 50 90                                                 42 125 60 70 100 100 50 50 70                                                 43 62.5 40 80 90 100 30 70 70                                                 44 125 70 40 100 100 50 70 90                                                 45 125 50 70 100 100 50 40 70                                                 46 60 60 90 100 50 50 100 40                                                  47 31.3 70 95 100 100 55 80 95                                                48 7.8 75 90 100 100 65 40 80                                                 49 15.6 75 95 100 100 75 75 80                                                50 62.5 65 95 95 100 65 70 80                                                 51 125 70 60 100 100 50 70 50                                                 52 62.5 80 95 100 100 40 80 100                                               53 31.3 75 90 100 100 65 70 80                                                54 31.3 70 95 100 100 60 30 90                                              __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm GWBLG GWBRN GWCRB GWGFT GWROX GWWOT                                 __________________________________________________________________________      26 31.3 75 85 60 100 100 100                                                  27 31.3 30 90 70 100 75 55                                                    28 15.6 80 95 100 100 100 80                                                  29 31.3 45 85 65 75 90 70                                                     30 125 30 85 30 70 80 40                                                      31 15.6 20 95 55 70 95 40                                                     32 31.3 20 75 70 70 90 30                                                     33 31.3 65 100 80 95 100 85                                                   34 31.3 15 90 70 75 75 40                                                     35 125 80 100 80 90 100 95                                                    36 15.6 85 100 85 100 100 100                                                 37 15.6 80 95 80 100 100 100                                                  38 31.3 95 100 85 100 100 100                                                 39 125 60 100 90 90 100 90                                                    40 62.5 85 70 85 80 100 100                                                   41 62.5 10 100 60 90 100 70                                                   42 125 10 90 30 100 100 50                                                    43 62.5 30 90 90 100 100 80                                                   44 125 50 90 50 90 100 70                                                     45 125 90 90 80 90 100 100                                                    46 60 40 60 90 100 100 90                                                     47 31.3 55 90 70 85 85 45                                                     48 7.8 70 95 65 100 100 70                                                    49 15.6 80 100 85 80 95 95                                                    50 62.5 0 90 75 90 90 65                                                      51 125 15 100 15 90 100 50                                                    52 62.5 45 100 75 100 100 75                                                  53 31.3 80 95 70 95 100 70                                                    54 31.3 70 90 70 80 100 60                                                  __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm BWCHK BWCKB BWLMQ BWPIG BWVIO BWWBK BWWPT                           __________________________________________________________________________      55 15.6 70 95 100 80 30 65 75                                                 56 15.6 75 90 85 100 60 25 80                                                 57 62.5 60 80 100 100 50 60 80                                                58 62.5 80 60 100 70 80 70 40                                                 59 15.6 75 80 100 100 40 80 75                                                60 31.3 70 80 80 100 20 20 75                                                 61 125 70 95 100 100 55 40 90                                                 62 62.5 85 90 100 100 70 80 95                                                63 125 70 70 90 70 70 70 80                                                   64 31.3 80 95 100 95 50 50 80                                                 65 125 70 70 90 40 70 40 70                                                   66 125 50 15 100 100 50 30 40                                                 67 62.5 50 85 90 100 60 60 50                                                 68 31.3 75 100 100 80 90 70 75                                              __________________________________________________________________________    Cpd.                                                                             Rate,                                                                        No. ppm GWBLG GWBRN GWCRB GWGFT GWROX GWWOT                                 __________________________________________________________________________      55 15.6 40 75 90 75 100 85                                                    56 15.6 75 95 80 100 100 90                                                   57 62.5 50 70 70 70 100 70                                                    58 62.5 60 85 70 90 100 85                                                    59 15.6 0 60 55 75 100 55                                                     60 31.3 55 95 70 85 75 85                                                     61 125 40 85 55 70 65 65                                                      62 62.5 70 90 100 100 90 85                                                   63 125 80 80 85 90 100 90                                                     64 31.3 0 80 55 70 75 10                                                      65 125 85 90 40 90 100 85                                                     66 125 60 90 10 90 90 30                                                      67 62.5 90 90 30 90 70 100                                                    68 31.3 60 90 80 100 100 80                                                 __________________________________________________________________________     BWCHK = chickweed (Stellaria media)                                           BWCKB = cocklebur (Xanthium strumarium)                                       BWLMQ = lambsquarters (Chenopodium album)                                     BWPIG = pigweed (Amaranthus retroflexus)                                      BWVIO = field pansy (Viola tricolor)                                          BWWBK = wild buckwheat (Polygonum convolvulus)                                BWWPT = wild poinsettia (Euphorbia heterophylla)                              GWBLG = blackgrass (Alopecurus myosuroides)                                   GWBRN = barnyardgrass (Echinochloa crusgalli)                                 GWCRB = crabgrass (Digitaria sanguinalis)                                     GWGFT = giant foxtail (Setaria faberi)                                        GWROX = Rox orange sorghum (Sorghum bicolor)                                  GWWOT = wild oats (Avena fatua)                                          

16. Evaluation of Preemergence Herbicidal Activity

Seeds of the desired test plant species were planted in a soil matrixprepared by mixing a loam soil which was composed of about 43 percentsilt, 19 percent clay, and 38 percent sand and had a pH of about 8.1 andan organic matter content of about 1.5 percent and sand in a 70 to 30ratio. The soil matrix was contained in plastic pots with a surface areaof 161 square centimeters. When required to ensure good germination andhealthy plants, a fungicide treatment and/or other chemical or physicaltreatment was applied.

A weighed amount, determined by the highest rate to be tested, of eachtest compound was placed in a 20 mL glass vial and was dissolved in 8 mLof a 97:3 v/v (volume/volume) mixture of acetone and dimethyl sulfoxideto obtain concentrated stock solutions. If the test compound did notdissolve readily, the mixture was warmed and/or sonicated. The stocksolutions obtained were diluted with a 99.9:0.1 mixture of water andTween® 155 surfactant to obtain application solutions of knownconcentration. The solutions containing the highest concentration to betested were prepared by diluting 4 mL aliquots of the stock solutionwith 8.5 mL of the mixture and lower concentrations were prepared bydilution of appropriate smaller portions of the stock solution. A 2.5 mLaliquot of each solution of known concentration was sprayed evenly ontothe soil of each seeded pot using a Cornwall 5.0 mL glass syringe fittedwith a TeeJet TN-3 hollow cone nozzle to obtain thorough coverage of thesoil in each pot. Control pots were sprayed in the same manner with theaqueous mixture. A highest application rate of 4.48 Kg/Ha is achievedwhen 50 mg of test compound is employed.

The treated pots and control pots were placed in a greenhouse with anapproximately 15 hr photoperiod which was maintained at about 23-29° C.during the day and 22-28° C. during the night. Nutrients and water wereadded on a regular basis and supplemental lighting was provided withoverhead metal halide 1000 Watt lamps as necessary. The water was addedby top-irrigation. After 3 weeks the condition of the test plants thatgerminated and grew as compared with that of the untreated plants thatgerminated and grew was determined visually and scored on a scale of 0to 100 percent where 0 corresponds to no injury and 100 corresponds tocomplete kill or no germination. Some of the compounds tested,application rates employed, plant species tested, and results are givenin Table 4.

                                      TABLE 4                                     __________________________________________________________________________    PREEMERGENCE HERBICIDAL ACTIVITY                                              Cpd.                                                                              Rate,                                                                       No. Kg/Ha BWCKB BWLMQ BWPIG BWVEL BWWPT GWBLG GWBRN GWCRB GWGFT GWROX                                                                 GWWOT               __________________________________________________________________________     5  0.07                                                                              40   100  100  100  25   50   70   100  75   100  40                     6 0.28 80 100 100 100 40 25 20 100 55 100 40                                  8 0.14 75 100 100 100 60 --  5 70 --  100 15                                  9 0.14 70 100 100 100 55 -- 15 70 -- 100 15                                  10 0.14 100 100 100 100 30 -- 70 80 50 100 80                                 11 0.14 65 100 90 98 95 -- 15 100 60 98 75                                    12 0.28 --  100 100 100 60 100 45 100 70 65 0                                 13 0.07 -- 100 100 100 60 10 85 70 85 100 40                                  14 0.14 -- 100 70 55 40 100 100 100 85 70 80                                  15 0.14 -- 100 100 100 65 0 80 100 95 100 65                                  16 0.14 100 100 100 100 60 30 30 100 60 100 65                                17 0.07 50 100 100 80 50 0 85 100 100 75 35                                   18 0.28 100 100 100 100 100 50 95 100 65 100 100                              19 0.28 90 100 100 100 80 30 20 100 100 90 90                                 20 0.28 90 100 100 100 100 30 80 100 40 80 90                                 21 0.14 55 100 0 25 25 20 45 100 100 100 30                                   23 0.28 90 100 100 75 65 60 0 70 45 70 0                                      24 0.035 45 100 100 100 50 30 55 100 100 75 70                                25 0.28 100 100 100 100 95 0 30 60 70 60 0                                    29 0.28 100 100 100 100 50 0 25 75 85 30 40                                   30 0.28 100 100 100 50 30 30 60 100 100 65 0                                  31 0.28 100 100 100 80 85 25 70 70 100 100 30                                 32 0.28 50 100 50 30 20 0 10 50 10 20 20                                      33 0.28 30 100 100 20 50 10 20 100 100 90 90                                  34 0.28 100 100 100 65 50 20 60 70 0 80 40                                    35 0.14 30 65 100 60 20 40 30 100 100 100 40                                  41 0.28 100 100 100 45 70 0 0 80 35 100 30                                    42 0.28 80 100 70 40 40 0 0 100 75 100 0                                      43 0.28 55 100 100 50 40 60 0 60 100 100 50                                   44 0.14 40 100 100 100 20 20 25 100 100 100 40                                45 0.28 40 100 100 85 0 45 0 100 100 100 85                                   46 0.14 30 100 100 100 25 30 25 100 100 100 15                                48 0.07 25 100 100 100 65 50 70 100 100 100 20                                49 0.14 70 100 100 100 70 50 100 100 100 90 70                                50 0.28 20 100 100 40 20 0 0 10 78 10 10                                      51 0.14 100 100 80 100 20 40 0 60 50 100 40                                   53 0.56 100 100 100 100 50 80 95 100 100 95 80                                54 0.56 20 10 100 100 100 20 20 100 10 100 10                                 55 0.28 30 100 100 100 50 0 90 100 100 100 50                                 56 0.28 10 100 100 100 20 10 30 100 100 90 30                                 57 0.07 40 75 100 100 10 15 100 100 100 100 20                                58 0.28 95 100 75 100 30 35 100 100 100 100 50                                66 0.14 100 100 100 100 55 30 10 80 55 100 60                                 67 0.14 100 100 100 100 45 80 60 100 100 100 100                            __________________________________________________________________________     BWCKB = cocklebur (Xanthium strumarium)                                       BWLMQ = lambsquarters (Chenopodium album)                                     BWMGL = morningglory (Ipomoea hederacea)                                      BWPIG = pigweed (Amaranthus retroflexus)                                      BWVEL = velvetleaf (Abutilion theophrasti)                                    BWWPT = wild poinsettia (Euphorbia heterophylla)                              GWBLG = blackgrass (Alopecurus myosuroides)                                   GWBRN = barnyardgrass (Echinochloa crusgalli)                                 GBCRB = crabgrass (Digitaria sanguinalis)                                     GWGFT = giant foxtail (Setaria faberi)                                        GWROX = Rox orange sorghum (Sorghum bicolor)                                  GWWOT = wild oats (Avena fatua)                                          

What is claimed is:
 1. A benzoylpyrazole compound of the formula:##STR16## wherein X represents F, Cl, Br, CH₃, C₂ H₅, or OCH₃ ;Yrepresents CH₃, C₂ H₅, CH(CH₃)₂, or cyclo-C₃ H₅ ; Z represents H orbenzyl (optionally possessing up to three ring substituents selectedfrom F, Cl, Br, CN, CF₃, NO₂, CH₃, C₂ H₅, OCH₃, and OC₂ H₅); Wrepresents F, Cl, Br, CN, NO₂, OH, R", OR", OCOR", OCONHR", OSO₂ R",SR", SOR", SO₂ R", SO₂ OR", SO₂ NHR", SO₂ NR"₂, NHR", NR"₂, CO₂ R",CONHR", or CONR"₂ ; or any two adjacent W together represent thefragment --O(CH₂)_(m) O-- optionally mono to completely substituted withfluorine or methyl; n represents 0, 1, 2, or 3; m represents 1, 2, or 3;R represents C₁ -C₄ alkyl, C₃ -C₄ alkenyl, or C₃ -C₄ alkynyl; R'represents H, CH₂ OCH₃, or C₁ -C₃ alkyl; R" represents C₁ -C₄ alkyl, C₂-C₄ alkenyl, or C₂ -C₄ alkynyl each optionally mono to completelysubstituted with fluorine or mono substituted with Cl, Br, O(C₁ -C₂alkyl), or S(C₁ -C₂ alkyl); andwhen Z represents H, the agriculturallyacceptable salts and esters thereof.
 2. A compound according to claim 1wherein Z represents hydrogen or an agriculturally acceptable salt orester of said compound.
 3. A compound according to claim 1 wherein Yrepresents methyl.
 4. A compound according to claim 1 wherein Xrepresents methyl.
 5. A compound according to claim 1 wherein R'represents hydrogen.
 6. A compound according to claim 1 wherein Rrepresents methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, orcyclo-propyl.
 7. A compound according to claim 6 wherein R represents1,1-dimethylethyl.
 8. A compound according to claim 1 wherein Wrepresents fluoro, chloro, methyl, ethyl, hydroxy, methoxy, ethoxy,1-methylethoxy, 2-propenyloxy, or methoxymethoxy.
 9. A compoundaccording to claim 1 wherein n represents 1 and the substituent islocated in the 4-position.
 10. A compound according to claim 9 wherein Wrepresents methoxy, ethoxy, 1-methylethoxy, or methoxymethoxy.
 11. Acompound according to claim 9 selected from1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethoxyphenyl)benzoyl)pyrazole,and1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxymethoxyphenyl)benzoyl)pyrazole.12. A composition comprising an herbicidally effective amount of anbenzoylpyrazole compound of the formula: ##STR17## wherein X representsF, Cl, Br, CH₃, C₂ H₅, or OCH₃ ;Y represents CH₃, C₂ H₅, CH(CH₃)₂, orcyclo-C₃ H₅ ; Z represents H or benzyl (optionally possessing up tothree ring substituents selected from F, Cl, Br, CN, CF₃, NO₂, CH₃, C₂H₅, OCH₃, and OC₂ H₅); W represents F, Cl, Br, CN, NO₂, OH, R", OR",OCOR", OCONHR", OSO₂ R", SR", SOR", SO₂ R", SO₂ OR", SO₂ NHR", SO₂ NR"₂,NHR", NR"₂, CO₂ R", CONHR", or CONR"₂ ; or any two adjacent W togetherrepresent the fragment --O(CH₂)_(m) O-- optionally mono to completelysubstituted with fluorine or methyl; n represents 0, 1, 2, or 3; mrepresents 1, 2, or 3; R represents C₁ -C₄ alkyl, C₃ -C₄ alkenyl, or C₃-C₄ alkynyl; R' represents H, CH₂ OCH₃, or C₁ -C₃ alkyl; R" representsC₁ -C₄ alkyl, C₂ -C₄ alkenyl, or C₂ -C₄ alkynyl each optionally mono tocompletely substituted with fluorine or mono substituted with Cl, Br,O(C₁ -C₂ alkyl), or S(C₁ -C₂ alkyl); andwhen Z represents H, theagriculturally acceptable salts and esters thereof in combination withan agriculturally acceptable adjuvant or carrier.
 13. A compositionaccording to claim 12 wherein Z represents hydrogen or an agriculturallyacceptable salt or ester of said compound.
 14. A composition accordingto claim 12 wherein Y represents methyl.
 15. A composition according toclaim 12 wherein X represents methyl.
 16. A composition according toclaim 12 wherein R' represents hydrogen.
 17. A composition according toclaim 12 wherein R represents methyl, ethyl, 1-methylethyl,1,1-dimethylethyl, or cyclo-propyl.
 18. A composition according to claim17 wherein R represents 1,1-dimethylethyl.
 19. A composition accordingto claim 12 wherein W represents fluoro, chloro, methyl, ethyl, hydroxy,methoxy, ethoxy, 1-methylethoxy, 2-propenyloxy, or methoxymethoxy.
 20. Acomposition according to claim 12 wherein n represents 1 and thesubstituent is located in the 4-position.
 21. A composition according toclaim 20 wherein W represents methoxy, ethoxy, 1-methylethoxy, ormethoxymethoxy.
 22. A composition according to claim 21 wherein thebenzoylpyrazole compound is selected from1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethoxyphenyl)benzoyl)pyrazole,and1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxymethoxyphenyl)benzoyl)pyrazole.23. A method of controlling undesirable vegetation which comprisescontacting the vegetation or the locus thereof with an herbicidallyeffective amount of an benzoylpyrazole compound of the formula:##STR18## wherein X represents F, Cl, Br, CH₃, C₂ H₅, or OCH₃ ;Yrepresents CH₃, C₂ H₅, CH(CH₃)₂, or cyclo-C₃ H₅ ; Z represents H orbenzyl (optionally possessing up to three ring substituents selectedfrom F, Cl, Br, CN, CF₃, NO₂, CH₃, C₂ H₅, OCH₃, and OC₂ H₅); Wrepresents F, Cl, Br, CN, NO₂, OH, R", OR", OCOR", OCONHR", OSO₂ R",SR", SOR", SO₂ R", SO₂ OR", SO₂ NHR", SO₂ NR"₂, NHR", NR"₂, CO₂ R",CONHR", or CONR"₂ ; or any two adjacent W together represent thefragment --O(CH₂)_(m) O-- optionally mono to completely substituted withfluorine or methyl; n represents 0, 1, 2, or 3; m represents 1, 2, or 3;R represents C₁ -C₄ alkyl, C₃ -C₄ alkenyl, or C₃ -C₄ alkynyl; R'represents H, CH₂ OCH₃, or C₁ -C₃ alkyl; R" represents C₁ -C₄ alkyl, C₂-C₄ alkenyl, or C₂ -C₄ alkynyl each optionally mono to completelysubstituted with fluorine or mono substituted with Cl, Br, O(C₁ -C₂alkyl), or S(C₁ -C₂ alkyl); andwhen Z represents H, the agriculturallyacceptable salts and esters thereof.
 24. A method according to claim 23wherein Z represents hydrogen or an agriculturally acceptable salt orester of said compound.
 25. A method according to claim 23 wherein Yrepresents methyl.
 26. A method according to claim 23 wherein Xrepresents methyl.
 27. A method according to claim 23 wherein R'represents hydrogen.
 28. A method according to claim 23 wherein Rrepresents methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, orcyclo-propyl.
 29. A method according to claim 28 wherein R represents1,1-dimethylethyl.
 30. A method according to claim 23 wherein Wrepresents fluoro, chloro, methyl, ethyl, hydroxy, methoxy, ethoxy,1-methylethoxy, 2-propenyloxy, or methoxymethoxy.
 31. A method accordingto claim 23 wherein n represents 1 and the substituent is located in the4-position.
 32. A method according to claim 31 wherein W representsmethoxy, ethoxy, 1-methylethoxy, or methoxymethoxy.
 33. A methodaccording to claim 32 wherein the benzoylpyrazole compound is selectedfrom1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxyphenyl)benzoyl)pyrazole,1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-ethoxyphenyl)benzoyl)pyrazole,and1-(1,1-dimethylethyl)-5-hydroxy-4-(2-methyl-4-methylsulfonyl-3-(4-methoxymethoxyphenyl)benzoyl)pyrazole.34. A method according to claim 23 wherein the undesirable vegetation iscontacted postemergently.
 35. A method according to claim 23 wherein theundesirable vegetation is contacted in the presence of a wheat, barley,or rice crop.
 36. A benzoylpyrazole compound of the formula: ##STR19##wherein X represents F, Cl, Br, CH₃, C₂ H₅, or OCH₃ ; andY representsCH₃, C₂ H₅, CH(CH₃)₂, or cyclo-C₃ H₅.
 37. A compound according to claim36 wherein X represents methyl.
 38. A compound according to claim 36wherein Y represents methyl.
 39. A composition according to claim 36wherein R' represents hydrogen.
 40. A composition according to claim 36wherein R represents methyl, ethyl, 1-methylethyl, 1,1-dimethylethyl, orcyclo-propyl.
 41. A composition according to claim 36 wherein Rrepresents 1,1-dimethylethyl.